Semiconductor device member, production method of semiconductor-device-member formation liquid and semiconductor device member, and semiconductor-device-member formation liquid, phosphor composition, semiconductor light-emitting device, lighting system and image display system using the same

ABSTRACT

To provide a semiconductor device member that is superior in heat resistance, light resistance, film-formation capability and adhesion, and is capable of sealing a semiconductor device and holding a phosphor without causing cracks, peelings and colorings even after used for a long period of time, the weight loss at the time of heating, measured by a predetermined weight-loss at-the-time-of-heating measurement method, is 50 weight % or lower and the ratio of peeling, measured by a predetermined adhesion evaluation method, is 30% or lower, in the semiconductor device member.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation application of U.S. application Ser.No. 12/438,283, filed on Apr. 2, 2009, which is a 371 of PCT/JP07/66310,filed on Aug. 27, 2007, and claims priority to the followingapplications: Japanese Patent Application No. 2006-225410, filed on Aug.22, 2006.

TECHNICAL FIELD

The present invention relates to a novel semiconductor device member, toa production method of a semiconductor-device-member formation liquidand a semiconductor device member, and to a semiconductor light-emittingdevice, a semiconductor-device-member formation liquid and a phosphorcomposition. More specifically, the present invention relates to asemiconductor device member that is superior in heat resistance, lightresistance, film-formation capability and adhesion, to a productionmethod of a semiconductor-device-member formation liquid and asemiconductor device member, and to a semiconductor light-emittingdevice with a large-size semiconductor element that can be used at hightemperatures. In addition, the present invention relates to a lightingsystem and an image display which are formed using the above-mentionedsemiconductor light-emitting device.

BACKGROUND ART

In a semiconductor device, especially in a semiconductor light-emittingdevice such as a light emitting diode (hereinafter abbreviated as “LED”when appropriate) and a semiconductor laser, a semiconductor element(this is also referred to as “semiconductor luminous element”) isgenerally sealed by a transparent member (semiconductor device member)made of resin or the like.

In recent years, the above-mentioned semiconductor light-emittingdevices have been put to practical use as information displays usedoutdoors, such as traffic lights and outdoor displays, automotiveheadlights, and lighting systems, in place of incandescent lamps andfluorescent lamps, because of their high emission efficiency,viewability, ruggedness and the like. However, it is preferable to use ahigh-power light emitting device (so-called, a “power device”) for thosepurposes. As a high-power semiconductor light-emitting device, asemiconductor element (chip) measuring 1 mm per side was disclosed, forexample, (Non-Patent Document 1). However, it has been difficult to usea semiconductor light-emitting device generally as power device.Therefore, plurally-provided low-power elements have been usedconventionally to circumvent the difficulty.

The reason why semiconductor light-emitting devices are difficult to beused generally as power devices is as follows. Namely, in order toincrease light output of an LED, for example, the electric power to besupplied should be increased first. However, heat generation also comesto be increased, with increase in electric power supplied. If the LEDchip is upsized, for the purpose of preventing increase in heat density,there will be unevenness in thermal expansion coefficients of thesealant and the chip, leading to low adhesion, as peeling of the sealantfrom the chip.

Epoxy resin, for example, has been used conventionally as theaforementioned semiconductor device member. In addition, a sealing resinthat contains a pigment such as a phosphor so as to convert the luminouswavelength of the light emitted from the semiconductor element has alsobeen known.

However, due to high hygroscopicity of epoxy resin, there have beenproblems of cracks caused by heat from the semiconductor element whenthe semiconductor device is used for a long time and degradation of thephosphor or the luminous element caused by moisture infiltration.

Also in recent years, with shortening of the luminous wavelength, therehas been a problem of dramatic decrease in brightness of thesemiconductor device because the epoxy resin degrades and colors whenthe device is used illuminated for a long time at a high output level.

In view of these problems, silicone resin, which is superior in heatresistance and ultraviolet-ray resistance, has been used as a substitutefor epoxy resin. However, silicone resin does not yet have sufficientadhesion, transparency and weather resistance. Meanwhile, inorganicsealants, which are materials excelling in heat resistance andultraviolet-ray resistance, and semiconductor devices using suchsealants have been proposed (Refer, for example, to Patent Documents 1to 6).

-   Non-Patent Document 1: Yukio Narikawa et al., “Oyo Butsuri”, Vol.    74, 11th issue, p. 1423 to p. 1432, 2005-   Patent Document 1: Japanese Patent Publication No. 3275308-   Patent Document 2: Japanese Patent Laid-Open Publication No.    2003-197976-   Patent Document 3: Japanese Patent Laid-Open Publication No.    2004-231947-   Patent Document 4: Japanese Patent Laid-Open Publication No.    2002-33517-   Patent Document 5: Japanese Patent Laid-Open Publication No.    2002-203989-   Patent Document 6: Description of Japanese Patent Application No.    2006-047274

DISCLOSURE OF THE INVENTION Problem to be Solved by the Invention

However, the treatment temperature of inorganic materials such as moltenglass is as high as 350° C. or more and thus luminous elements will bedamaged. Therefore, use of them as inorganic sealants has not beenindustrially realized.

On the other hand, glasses produced by sol gel methods have a problem offilm-formation capability, such as crack generation and peeling, due toshrinkage on curing at the time of molding as semiconductor devicemember. Therefore, no such kind of glasses whose thick film state isstable over a long period of time have not yet been obtained.

Since the reactivity in sol-gel production methods is extremely high,condensation is difficult, and therefore, a large amount of solvent isoften used. A large amount of solvent reduces the ratio of the solidportion of the sol. Therefore, when producing a semiconductor devicemember by applying the sol on a semiconductor device, it should beapplied repeatedly until it reaches a predetermined thickness. Thisleads to low production efficiency. In addition, since the solvent isvolatilized during the curing, an internal stress is liable to begenerated in the cured semiconductor device member, leading frequentlyto crack generations and peelings. It is also unfavorable from thestandpoint of burden on the environment.

Furthermore, these inorganic sealants are very hard and fragile, andtherefore they are insufficient in film-formation capability. This leadsto a problem of frequent generations of peelings, cracks and breaking ofwires during use, since they can not follow the thermal expansion andthermal shrinkage of each of the members, which are different in thermalexpansion coefficient, used in the semiconductor device. Those excellingin reflow resistance and temperature cycling resistance have not yetbeen realized, either. In this context, reflow means a soldering processin which soldering pastes are printed on a substrate and components aremounted thereon so as to be heated and connected. The above reflowresistance means a characteristic of ability to resist the thermal shockof up to 260° C. for 10 seconds.

For example, Patent Documents 1 and 2 describe a technology for forminga glass material using tetrafunctional alkoxysilane. However, ininorganic materials obtained from the technologies described in PatentDocuments 1 and 2, a hydrolyzing liquid of tetrafunctional alkoxysilanewas coated on a semiconductor light-emitting device and cured forseveral hours at a mild cure temperature of about 150° C., which doesnot damage performance of the semiconductor light-emitting device. Inthese cases, the obtained glass material was an incomplete glass bodythat usually contains more than 10 weight % of silanol. Thus, it hasbeen impossible to obtain a glass body consisting entirely of siloxanebonds like molten glasses, by the technologies described in PatentDocuments 1 and 2.

The reason is considered as follows. In contrast to general organicresins, the inorganic materials used in Patent Documents 1 and 2 havequite a lot of crosslinking points and therefore, the constraints bystructure are considerable and the reactive ends cannot be condensedsince they are isolated. Since such a glass body is not fine and thesurface thereof is in a very highly hydrophilic state like silica gel,the glass body does not have sufficient sealing properties.

Such less reactive silanol generally starts to decrease very slightlywhen heated up to 250° C. or higher, and by burning the inorganicmaterial at a high temperature of normally 350° C. or higher andpreferably 400° C. or higher, the amount of silanol can actively bereduced. However, even if an attempt is made to remove silanol from theinorganic materials described in Patent Documents 1 and 2 using theabove process, its realization is difficult to achieve because theheat-resistant temperature of a semiconductor device is normally 260° C.or lower.

Further, since tetrafunctional alkoxysilane eliminates a large amount ofcomponents during dehydration/dealcoholization condensation, theshrinkage factor during curing is substantially large. Moreover, becauseof high reactivity of tetrafunctional alkoxysilane, in the dryingprocess, its curing starts from a surface portion from which part of adiluent solvent has evaporated and there is a tendency of forming a hardgel body including a solvent before discharging the internal solvent.This leads to a large shrinkage amount accompanying the solventevaporation during and after the curing. Thus, inorganic materialsdescribed in Patent Documents 1 and 2 result in frequent cracks due tolarge internal stress caused by the shrinkage. Therefore, it has beendifficult to obtain a large bulk body or thick film that is useful as asemiconductor device member using only tetrafunctional alkoxysilane asits material.

Also, for example, Patent Document 3 describes a technology forproducing a three-dimensional phosphor layer with good dimensionalaccuracy by sol gel method using a silane compound containing organicgroups as material. However, there is no detailed description of thedegree of crosslinking in Patent Document 3, and high-concentrationphosphor particles are required to obtain the inorganic materialdescribed in Patent Document 3. Since these phosphor particles actsubstantially as an aggregate to maintain the three-dimensional shape,no thick-film glass coated article that is transparent and contains nocracks has been obtainable without any phosphor contained in theinorganic material.

Further, acetic acid is used as catalyst in the technology of PatentDocument 3. However, because acetic acid is not removed from theresultant inorganic material, the acetic acid affects a semiconductorelement adversely. In addition, when forming the inorganic materialdescribed in Patent Document 3, it is practically impossible to heat theinorganic material together with a semiconductor device because itscuring process requires a high temperature of 400° C. Furthermore,distortions in its structure are accumulated due to impracticalcondensation at high temperatures, and therefore, crack generations arenot suppressed.

Also, for example, Patent Document 4 describes a technology forobtaining a semiconductor device member by means of coating with aninorganic coating agent that is obtained by mixing an inorganic solhaving silica or siloxane as its skeletal structure with an inorganiclight scattering agent. However, the inorganic material described inPatent Document 4 requires an inorganic light scattering agent, andfurther, Patent Document 4 provides no detailed description of thematerial and producing method thereof. This makes it impossible tocorrectly reproduce the technology.

Further, for example, Patent Document 5 describes a technology forobtaining a semiconductor device member by means of coating with a solgel method glass. However, in the same way as in Patent Document 3, aphosphor is necessary to obtain the inorganic material described inPatent Document 5. In addition, though a resultant inorganic material isa thick film, due to the fact that the phosphor acts as an aggregate,the film thickness does not exceed 100 μm. Furthermore, Patent Document5 provides no detailed description of the material and producing methodthereof, and thus it is impossible to steadily reproduce the technologyusing a general alkoxysilane.

In addition, the present inventors disclosed specific silicon-containingsemiconductor device member that can solve the above-mentioned problemsin Patent Document 6. However, it has been desirable to improve the heatstability further, while maintaining the light resistance,film-formation capability and adhesion, when it is used for asemiconductor power device, which is high in heat dissipation. It hasalso been desirable to inhibit the volatilization of the low-boilingimpurities so as to enhance the yield by weight of the cured product inthe manufacturing process of the semiconductor device member.

Moreover, various surface treatments are provided on a package of asemiconductor light-emitting device for the purpose of improvingbrightness (reflectance), durability/heat resistance, light resistance,adhesion, heat dissipating property and the like. In particular, powerdevices are often subjected to a surface treatment and the materialthereof is often selected for the purpose of improving durability andheat resistance. In addition, a semiconductor element (chip) is oftenprovided with a protective layer from the standpoint of manipulation orthe like. In these ways, the surface materials of members that are incontact with the sealant in the semiconductor light-emitting device,such as the package and the semiconductor element, contain a peculiarcomponent. This leads to a further cause for accelerating a problem ofpeeling.

With circumstances described above as a background, a semiconductordevice member that is superior in heat resistance, light resistance,film-formation capability and adhesion, and is capable of sealing asemiconductor device and holding a phosphor without causing cracks,peelings and colorings even after used for a long period of time hasbeen demanded.

The present invention has been made in view of the above problems.Namely, the first object of the present invention is to provide a novelsemiconductor device member that is superior in heat resistance, lightresistance, film-formation capability and adhesion, and is capable ofsealing a semiconductor device and holding a phosphor without causingcracks, peelings and colorings even after used for a long period oftime, a production method of a semiconductor-device-member formationliquid and a semiconductor device member, and asemiconductor-device-member formation liquid and a phosphor compositionusing the same. The second object of the present invention is to providea semiconductor light-emitting device without cracks and peelingsgenerated even after used for a long period of time and with superiorbrightness (reflectance), durability/heat resistance, light resistance,adhesion and the like even when used particularly for a power device,and a lighting system and an image display using the same.

Means for Solving the Problem

As a result of intensive investigation to achieve the above-mentionedobjects, the inventors made the following findings. That is, a specificpolymer that has small thermogravimetric reduction and a specifieddegree of film-formation capability can be formed into a thick film whenused as semiconductor device member, and even at the thick film portion,such a polymer can be reduced in crack generation and excellent in heatresistance and light resistance. In addition, a sealant that isextremely high in adhesion to a material of which surface is treated andexcellent in heat resistance and light resistance can be used even in apower device especially with a large-size semiconductor light-emittingchip. These findings have led to the completion of the presentinvention.

Namely, the subject matter of the present invention lies in asemiconductor device member whose weight loss at the time of heating,measured by the weight-loss at-the-time-of-heating measurement method(I) below, is 50 weight % or lower and ratio of peeling, measured by theadhesion evaluation method (II) below, is 30% or lower (claim 1).

Weight-Loss at-the-Time-of-Heating Measurement Method (I):

The weight loss is measured by a thermogravimetric/differential thermalanalyzer for a 10-mg fragment of the semiconductor device member when itis heated from 35° C. to 500° C. at a temperature rising rate of 10°C./min under 200-ml/min flow of air.

Adhesion Evaluation Method (II):

(1) A semiconductor-device-member formation liquid is dropped into asilver-plated copper cup having a diameter of 9 mm and a depth at therecess of 1 mm, and then cured under a predetermined curing condition,thereby preparing a semiconductor device member.(2) The obtained semiconductor device member is let absorb moisture inan atmosphere of 85-° C. temperature and 85-% humidity for 20 hours.(3) The semiconductor device member that absorbed moisture is heatedfrom room temperature to 260° C. in seconds, and then kept at 260° C.for 10 seconds.(4) The heated semiconductor device member is cooled to roomtemperature, and then the existence or the nonexistence of a peeling ofthe semiconductor device member from the above-mentioned copper cup isobserved both by visual inspection and with a microscope.(5) The ratio of peeling of the semiconductor device member isdetermined by conducting the above operations (2), (3) and (4) for eachof 10 the semiconductor device members.

Another subject matter of the present invention lies in a semiconductordevice member whose weight loss at the time of heating, measured by theweight-loss at-the-time-of-heating measurement method (I) describedabove, is 50 weight % or lower and measurement value of hardness (ShoreA) by durometer type A is 5 or larger and 90 or smaller (claim 2).

In this case, it is preferable that the skeletal structure thereof is ametalloxane bond (claim 3).

Further, it is preferable that the semiconductor device member of thepresent invention contains inorganic particle (claim 4).

Further, it is preferable that the semiconductor device member of thepresent invention contains a phosphor (claim 5).

Still another subject matter of the present invention lies in aproduction method of a semiconductor-device-member formation liquidcontaining a polycondensate obtained by performing hydrolysis andpolycondensation of a compound represented by the following formula (1)and/or an oligomer thereof, wherein the hydrolysis and polycondensationare performed in the presence of an organometallic compound catalystcontaining at least one kind of element selected from zirconium,hafnium, tin, zinc and titanium (claim 6).

[Chemical Formula 1]

M^(m+)X_(n)Y¹ _(m−n)  (1)

(In the formula (1), M represents at least one element selected fromsilicon, aluminum, zirconium and titanium, X represents a hydrolyzablegroup, Y¹ represents a univalent organic group, m represents an integerof 1 or larger representing the valence of M, and n represents aninteger of 1 or larger representing the number of X groups, where m≧n.)

Still another subject matter of the present invention lies in aproduction method of a semiconductor-device-member formation liquidcontaining a polycondensate obtained by performing hydrolysis andpolycondensation of a compound represented by the following formula (2)and/or an oligomer thereof, wherein the hydrolysis and polycondensationare performed in the presence of an organometallic compound catalystcontaining at least one element selected from zirconium, hafnium, tin,zinc and titanium (claim 7).

[Chemical Formula 2]

(M^(s+)X_(t)Y¹ _(s−t−1))_(u)Y²  (2)

(In the formula (2), M represents at least one element selected fromsilicon, aluminum, zirconium and titanium, X represents a hydrolyzablegroup, Y¹ represents a univalent organic group, Y² represents a u-valentorganic group, s represents an integer of 2 or larger representing thevalence of M, t represents an integer of 1 or larger and s−1 or smaller,and u represents an integer of 2 or larger.)

Still another subject matter of the present invention lies in aproduction method of a semiconductor device member, comprising a step ofdrying a polycondensate obtained by performing hydrolysis andpolycondensation of a compound represented by the following formula (1)and/or an oligomer thereof, wherein the hydrolysis and polycondensationare performed in the presence of an organometallic compound catalystcontaining at least one element selected from zirconium, hafnium, tin,zinc and titanium (claim 8).

Still another subject matter of the present invention lies in aproduction method of a semiconductor device member, comprising a step ofdrying a polycondensate obtained by performing hydrolysis andpolycondensation of a compound represented by the following formula (2)and/or an oligomer thereof, wherein the hydrolysis and polycondensationare performed in the presence of an organometallic compound catalystcontaining at least one element selected from zirconium, hafnium, tin,zinc and titanium (claim 9).

Still another subject matter of the present invention lies in asemiconductor light-emitting device comprising at least thesemiconductor device member described above (claim 10) (sic).

Still another subject matter of the present invention lies in asemiconductor-device-member formation liquid produced by a productionmethod of semiconductor-device-member formation liquid described above(claim 11) (sic).

Still another subject matter of the present invention lies in asemiconductor light-emitting device comprising an (A) package, (B)semiconductor element and (C) sealant, wherein the surface materials ofthe (A) package and/or the (B) semiconductor element contain one or moreof Si, Al and Ag, and the (C) sealant is in direct contact with thesurface materials of the (A) package and/or the (B) semiconductorelement and satisfies all of the following conditions (i) to (iii)(claim 12).

(i) The sealant has a functional group capable of forming a hydrogenbond with an oxygen in a metalloxane bond or a hydroxyl group, which ispresent on the surface of a ceramic or a metal,

(ii) The maintenance rate of transmittance with respect to light of400-nm wavelength before and after kept at temperature of 200° C. for500 hours is 80 or more and 110% or less, and

(iii) The maintenance rate of transmittance with respect to the light of400-nm wavelength before and after being irradiated with light havingwavelength of 370 nm or longer and center wavelength of 380 nm andradiant intensity of 0.6 kW/m² for 72 hours is 80% or more and 110% orless.

In this case, it is preferable that the semiconductor light-emittingdevice of the present invention further satisfies the followingcondition (iv) (claim 13).

(iv) The ratio of brightness after 500 hours illumination, in which asquare semiconductor element measuring 900 μm per side having 460±10 nmof luminous wavelength is illuminated at 85-° C. temperature and 85-%relative humidity for 500 hours in a continuous manner with 350 mA ofdriving current while maintaining the temperature of the emissionsurface at 100±10° C., relative to that of just after switched on is 90%or higher.

Further, it is preferable that the semiconductor light-emitting deviceof the present invention contains the (C) sealant of the semiconductordevice member of the present invention (claim 14).

Further, it is preferable that the surface materials of the (A) packageand/or the (B) semiconductor element contain one or more of SiN_(x), SiCand SiO₂ (claim 15).

Further, it is preferable that the surface materials of the (A) packageand/or the (B) semiconductor element contain one or more of Al, AlN andAl₂O₃ (claim 16).

Further, it is preferable that the (B) semiconductor element of thesemiconductor light-emitting device of the present invention containsthe surface material in its substrate part (claim 17).

Further, it is preferable that the area of the emission surface of the(B) semiconductor element of the semiconductor light-emitting device ofthe present invention is 0.15 mm² or larger (claim 18).

Further, it is preferable that the surface temperature of the emissionsurface of the (B) semiconductor element of the semiconductorlight-emitting device of the present invention during operation is 80°C. or higher and 200° C. or lower (claim 19).

Further, it is preferable that the amount of electric power duringoperation of the semiconductor light-emitting device of the presentinvention is 0.1 W or larger (claim 20).

Still another subject matter of the present invention lies in a lightingsystem formed using the semiconductor light-emitting device of thepresent invention (claim 21).

Still another subject matter of the present invention lies in an imagedisplay formed using the semiconductor light-emitting device of thepresent invention (claim 22).

Advantageous Effect of the Invention

The semiconductor device member of the present invention is superior inheat resistance, light resistance, film-formation capability andadhesion, and capable of sealing a semiconductor device without causingcracks or peelings even after used for a long period of time. Usually,it can be applied in a thicker film state than the previous inorganicsemiconductor device member. It can easily seal the semiconductor deviceand hold the phosphor just by applying it on the semiconductor deviceand drying it.

With the semiconductor-device-member formation liquid and the phosphorcomposition of the present invention, the semiconductor device member ofthe present invention can be produced.

By the production methods of the semiconductor-device-member formationliquid and the semiconductor device member of the present invention, thesemiconductor-device-member formation liquid and the semiconductordevice member of the present invention can be produced.

The semiconductor light-emitting device of the present invention canmaintain its performance for a long period of time without causingcracks, peelings or colorings even after used for a long time, becausethe sealant thereof is superior in heat resistance, light resistance,film-formation capability and adhesion.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic sectional view showing Embodiment A-1;

FIG. 2 is a schematic sectional view showing Embodiment A-2;

FIG. 3 shows Embodiment B-1, and FIG. 3( a) is a schematic sectionalview and FIG. 3( b) is an enlarged view of a substantial part of FIG. 3(a);

FIG. 4 is a schematic sectional view showing Embodiment B-2;

FIG. 5 is a schematic sectional view showing Embodiment B-3;

FIG. 6 is a schematic sectional view showing Embodiment B-4;

FIG. 7 is a schematic sectional view showing Embodiment B-5;

FIG. 8 is a schematic sectional view showing Embodiment B-6;

FIG. 9 is a schematic sectional view showing Embodiment B-7;

FIG. 10 is a schematic sectional view showing Embodiment B-8;

FIG. 11 is a schematic sectional view showing Embodiment B-9;

FIG. 12 is a schematic sectional view showing Embodiment B-10;

FIG. 13 is a schematic sectional view showing Embodiment B-11;

FIG. 14 is a schematic sectional view showing Embodiment B-12;

FIG. 15 is a schematic sectional view showing Embodiment B-13;

FIG. 16 is a schematic sectional view showing Embodiment B-14;

FIG. 17 is a schematic sectional view showing Embodiment B-15;

FIG. 18 is a schematic sectional view showing Embodiment B-16;

FIG. 19 is a schematic sectional view showing Embodiment B-17;

FIG. 20 is a schematic sectional view showing Embodiment B-18;

FIG. 21 is a schematic sectional view showing Embodiment B-19;

FIG. 22 is a schematic sectional view showing Embodiment B-20;

FIG. 23 is a schematic sectional view showing Embodiment B-21;

FIG. 24 is a sectional view of a substantial part, showing EmbodimentB-21;

FIG. 25 is a schematic sectional view showing Embodiment B-22;

FIG. 26 is a sectional view of a substantial part, showing EmbodimentB-22;

FIG. 27 is a schematic sectional view showing Embodiment B-23;

FIG. 28 is a perspective view of a substantial part, showing EmbodimentB-23;

FIG. 29 is a schematic sectional view showing Embodiment B-24;

FIG. 30 is a sectional view of a substantial part, showing EmbodimentB-24;

FIG. 31 is a perspective view of a substantial part, showing EmbodimentB-24;

FIG. 32 is a schematic sectional view showing Embodiment B-25;

FIG. 33 is a schematic sectional view showing Embodiment B-26;

FIG. 34 is a schematic sectional view showing Embodiment B-27;

FIG. 35 is a schematic sectional view showing Embodiment B-28;

FIG. 36 is a schematic sectional view showing Embodiment B-29;

FIG. 37 shows Embodiment B-30, and FIG. 37( a) is a schematic sectionalview and FIG. 37( b) is an enlarged view of a substantial part of FIG.37( a);

FIG. 38 is a schematic sectional view showing Embodiment B-31;

FIG. 39 is a schematic sectional view showing Embodiment B-32;

FIG. 40 is a schematic sectional view showing Embodiment B-33;

FIG. 41 is a schematic sectional view showing Embodiment B-34;

FIG. 42 is a schematic sectional view showing Embodiment B-35;

FIG. 43 is a schematic sectional view showing Embodiment B-36;

FIG. 44 is a schematic sectional view showing Embodiment B-37;

FIG. 45 is a schematic sectional view showing Embodiment B-38;

FIG. 46 is a schematic sectional view showing Embodiment B-39;

FIG. 47 is a schematic sectional view showing Embodiment B-40;

FIG. 48 is a schematic sectional view showing Embodiment A-41;

FIG. 49 is an explanatory drawing of another configuration example of asubstantial part of each Embodiment;

FIG. 50( a) and FIG. 50( b) are respectively explanatory drawings ofbasic concepts of each Embodiment; and

FIG. 51 is a sectional view showing schematically a semiconductorlight-emitting device for explaining continuous lighting tests, carriedout in Examples and Comparative Examples of the present invention.

EXPLANATION OF LETTERS OR NUMERALS

-   1, 1A, 1B Light emitting device (semiconductor light-emitting    device)-   2 Luminous element-   3A Transparent member (semiconductor light-emitting device member)-   3B Phosphor part (semiconductor light-emitting device member)-   4 a, 4 b Part of light emitted from a luminous element-   5 Light of wavelengths specific to phosphor components, such as    phosphor particles, fluorescent ions and fluorescent dyes, contained    in the phosphor part-   11 Mold part-   12, 13 Lead terminal-   14 Mirror (cup part)-   15 Conductive wire-   16 Insulating substrate-   16 a Hollow-   17 Printed wiring-   18 Frame-   19 Sealing part-   19 a Sealing function part-   19 b Lens function part-   19 c Recess-   19 d Through-hole-   21 Luminous layer part-   23 Reflecting layer-   24 Bump-   33, 34 Phosphor part-   35 Solid medium-   36 Lid-   101 Cup-   102 LED chip-   103 LED element (sic)

BEST MODES FOR CARRYING OUT THE INVENTION

The present invention will be described in detail below, but it is to beunderstood that the present invention is not limited to the embodimentshown below and any modification can be added thereto insofar as they donot depart from the scope of the present invention.

[1] Semiconductor Device Member

The first semiconductor device member of the present invention hascharacteristics (1) and (2) shown below.

Characteristic (1): The weight loss at the time of heating, measured bythe specific weight-loss at-the-time-of-heating measurement method (1)below, is 50 weight % or lower.

Characteristic (2): The ratio of peeling, measured by the specificadhesion evaluation method (II) below, is 30% or lower.

The second semiconductor device member of the present invention has theabove-mentioned characteristic (1) and the characteristic (3) shownbelow.

Characteristic (3): The measurement value of hardness (Shore A) bydurometer type A is 5 or larger and 90 or smaller.

In the following, these characteristics (1), (2) and (3) will beexplained first. In the following explanation, the first and secondsemiconductor device members of the present invention will be referredto simply as “the semiconductor device member of the present invention”when no distinction is made between them.

[1-1] Weight Loss at the Time of Heating

Weight loss at the time of heating is an index for evaluating thehigh-level heat resistance of the semiconductor device member of thepresent invention. It is measured by the weight-lossat-the-time-of-heating measurement method (I) to be described later.

The weight loss at the time of heating of the semiconductor devicemember of the present invention is 50 weight % or lower, preferably 40weight % or lower, and more preferably 35 weight % or lower, and thereis no lower limit specially, but it is usually 5 weight % or higher,preferably 10 weight % or higher (characteristic (1)). When the weightloss at the time of heating is too large, a long-term use of thesemiconductor device induces a shrinkage, leading possibly to failing inmaintenance of the initial performance. As the reason why the weightloss at the time of heating becomes large can be cited, for example, alarge amount of volatile low-molecular-weight component contained in thesemiconductor device member, a proneness to cleavage of the main chainwhich forms the semiconductor device member by heat, and so on. A smallamount of weight loss at the time of heating makes the semiconductordevice member superior in heat stability, but such a semiconductordevice member will be a hard film because it generally contains muchpolyfunctional Si component. Therefore, a semiconductor device memberwith too small weight loss at the time of heating is inferior in heatcycle resistance, reflow resistance and the like, which is notunfavorable for a semiconductor device member.

[Weight-Loss at-the-Time-of-Heating Measurement Method (I)]

The weight loss is measured by a thermogravimetry/differential thermalanalysis (hereinafter abbreviated as “TG-DTA” as appropriate) apparatusfor a 10-mg fragment of the above-mentioned semiconductor device memberwhen it is heated from 35° C. to 500° C. at a temperature rising rate of10° C./min under 200-ml/min flow of air.

Satisfying the following requirements, for example, can realize theabove-mentioned characteristic (1) of the semiconductor device member ofthe present invention.

(i) Selecting raw materials properly. For example, the materials havingconstructions described in [1-4-1], to be described later, can beselected, or the materials described in [2-1], to be described later,can be used.

(ii) Selecting catalysts in the process of hydrolysis andpolycondensation described in [2-2], to be described later.

(iii) Molecular weight control in the process of hydrolysis andpolycondensation described in [2-2], to be described later, and/orduring storage of the hydrolyzate/polycondensate.

[1-2] Adhesion

Ratio of peeling in the adhesion evaluation is an index for evaluatingthe adhesion of the semiconductor device member of the presentinvention. It is measured by the adhesion evaluation method (II) to bedescribed later.

The ratio of peeling of the semiconductor device member of the presentinvention is usually 30% or lower, preferably 20% or lower, and morepreferably 10% or lower (characteristic (2)). Among them, 0% is the mostpreferable. Too large ratio of peeling degrades the adhesion andchemical stability of the semiconductor device member against thesubstrate, frame or the like, leading possibly to proneness todenaturation or shrinkage of the sealant when it is subjected to atemperature shock or a thermal, optical or electrochemical reaction.This may lead to a peeling of the semiconductor device member from thesubstrate, frame or the like and a breaking of wire in the semiconductordevice. In addition, too low adhesion may induce a peeling of thesemiconductor device member from the surface of the electrode orreflector, which are often formed of a silver material particularly in asemiconductor light-emitting device, leading possibly to a breaking ofwire, failure in illumination and reduction in brightness of thesemiconductor light-emitting device.

[Adhesion Evaluation Method (II)]

(1) A semiconductor-device-member formation liquid (to be describedlater) is dropped into a silver-plated copper cup having a diameter of 9mm and a depth at the recess of 1 mm, and then cured under apredetermined curing condition, thereby preparing a semiconductor devicemember (hereinafter, this semiconductor device member is referred to as“sample for measurement” in the explanation for the adhesion evaluationmethod (II)).

(2) The obtained sample for measurement is let absorb moisture in anatmosphere of 85-° C. temperature and 85-% humidity for 20 hours.

(3) The sample for measurement that absorbed moisture was heated fromroom temperature to 260° C. in 50 seconds and then kept at 260° C. for10 seconds. In this context, the room temperature means 20° C. to 25° C.

(4) The heated sample for measurement is cooled to room temperature, andthen the existence or the nonexistence of a peeling of the sample formeasurement from the copper cup is observed both by visual inspectionand with a microscope. Even a sample observed to have just a smallpeeling is labeled as “peeling generated”.

(5) The ratio of peeling of the above-mentioned sample for measurementis determined by conducting the above operations (2), (3) and (4) foreach of 10 samples for measurement. In this context, the ratio ofpeeling is the ratio that can be calculated as “the number of samplesfor measurement in which a peeling is generated/the total number ofsamples for measurement”.

Satisfying the following requirements, for example, can realize theabove-mentioned characteristic (2) of the semiconductor device member ofthe present invention.

(i) Selecting raw materials properly. For example, the materials havingconstructions described in [1-4-1], to be described later, can beselected, or the materials described in [2-1], to be described later,can be used.

(ii) Selecting catalysts in the process of hydrolysis andpolycondensation described in [2-2], to be described later.

(iii) Molecular weight control in the process of hydrolysis andpolycondensation described in [2-2], to be described later, and/orduring storage of the hydrolyzate/polycondensate.

[1-3] Hardness Measurement Value

Hardness measurement value is an index for evaluating the hardness ofthe semiconductor device member of the present invention. It is measuredby the hardness measurement method described below.

The semiconductor device member of the present invention is preferably amember presenting elastomer properties. This is because a semiconductordevice uses a plurality of members whose thermal expansion coefficientsare different but the semiconductor device member of the presentinvention can relieve stress caused by expansion and contraction of eachof the above members with the elastomer properties described above.Therefore, a semiconductor device that is resistant to a peeling, crack,and breaking of wire while in use and superior in reflow resistance andtemperature cycling resistance can be provided.

More specifically, the hardness measurement value (Shore A) by durometertype A, of the semiconductor device member of the present invention, isusually 5 or larger, preferably 7 or larger, and still preferably 10 orlarger, and usually 90 or smaller, preferably 80 or smaller, and stillpreferably 70 or smaller (characteristic (3)). With the hardnessmeasurement value in the above range being provided, the semiconductordevice member of the present invention can obtain such an advantage asbeing more resistant to cracks and superior in reflow resistance andtemperature cycling resistance.

[Hardness Measurement Method]

The above hardness measurement value (Shore A) can be measured accordingto a method described in JIS K6253. More specifically, the measurementcan be made using an A-type rubber hardness scale manufactured by KoriSeiki MFG. Co., Ltd.

In this way, the first semiconductor device member of the presentinvention can realize a cured product that is superior in film-formationcapability, adhesion and resistance to light and heat after the curing,by exhibiting the characteristic (1) explained in [1-1] and thecharacteristic (2) explained in [1-2]. On the other hand, the secondsemiconductor device member of the present invention can also realize acured product that is superior in film-formation capability andresistance to light and heat after the curing, by exhibiting thecharacteristic (1) explained in [1-1] and the characteristic (3)explained in [1-3].

In addition, a semiconductor device member exhibiting all theabove-mentioned characteristics (1), (2) and (3) is more preferablebecause it satisfies all the requirements of the first and secondsemiconductor device members of the present invention.

[1-4 Other Physicochemical Properties]

The semiconductor device member of the present invention has theabove-mentioned major characteristics, but it is preferable that it hasalso additional structures and characteristics described in thefollowing.

[1-4-1] Basic Skeleton

The basic skeleton of the conventional semiconductor device member is anorganic resin such as an epoxy resin having carbon-carbon andcarbon-oxygen bonds as its basic skeleton. In contrast, it is preferablethat the basic skeleton of the semiconductor device member of thepresent invention is usually a metalloxane skeletal structure, andpreferably an inorganic siloxane skeletal structure (siloxane bond) likeglasses (silicate glasses). As is evident from Table 1 below, whichshows a comparison of chemical bonds, siloxane bonds have the followingsuperior features for a semiconductor device member.

(I) Having superior light resistance because the bond energy is largeand thus pyrolysis and photolysis rarely occur.(II) Electrically polarized slightly.(III) The chain structure thereof has a high degree of freedom, leadingto a highly flexible structure and free rotation about the siloxanechain.(IV) Highly oxidized so that further oxidization is impossible.(V) High in electrical insulating properties.

TABLE 1 Chemical bonds comparison table Bond Bond energy Bond angle Bonddistance (Å) (kcal/mol) (°) Si-O-Si 1.64 108 130 to 160 C-O-C 1.43  86110 C-C-C 1.54  85 109

From these features, it can be understood that a semiconductor devicemember based on silicon, which is formed by a skeletal structure inwhich siloxane bonds are connected three-dimensionally with a highdegree of crosslinking, can become a protective film that is similar tominerals such as glasses and rocks and excellent in heat resistance andlight resistance, in contrast to the conventional semiconductor devicemember based on a resin such as an epoxy resin. Particularly, asemiconductor device member based on silicon having a methyl group asits substituent is superior in light resistance, because such a memberdoes not have an absorption region in the ultraviolet region andtherefore photolysis is unlikely to occur.

The silicon content of the semiconductor device member of the presentinvention, when it comprises a siloxane skeletal structure, is usually20 weight % or more, preferably 25 weight % or more, and more preferably30 weight % or more. On the other hand, the upper limit thereof isusually 47 weight %, because the silicon content of a glass thatconsists only of SiO₂ is 47 weight %. Meanwhile, when the semiconductordevice member is intended to be high in refractive index, the abovecontent is usually 10 weight % or more and 47 weight % or less, since acomponent necessary for the higher refractive index may be contained.

The silicon content of a semiconductor device member can be calculatedbased on the result of inductively coupled plasma spectrometry(hereinafter abbreviated as “ICP” when appropriate) analysis accordingto, for example, the method described below.

[Measurement of Silicon Content]

A singly cured product of the semiconductor device member is ground topieces of about 100 μm and kept in a platinum crucible in the air at450° C. for 1 hour and then at 750° C. for 1 hour and at 950° C. for 1.5hours for firing. After removal of carbon components, the small amountof residue obtained is added with a 10-fold amount or more of sodiumcarbonate, and then heated by a burner to melt it. Then the meltedproduct is cooled and added with desalted water, being diluted toseveral ppm in silicon, while adjusting pH value to around neutralityusing hydrochloric acid. And then ICP analysis is performed.

[1-4-2] Silanol Content

The silanol content of the semiconductor device member of the presentinvention, when it comprises a siloxane skeletal structure, is in therange of usually 0.01 weight % or more, preferably 0.1 weight % or more,and more preferably 0.3 weight % or more, and usually 12 weight % orless, preferably 8 weight % or less, and more preferably 6 weight % orless.

A glass body produced by sol gel method from a material of alkoxysilaneusually does not completely polymerize to become an oxide under a mildcuring condition such as 150° C. of curing temperature and about threehours of curing time, and a certain amount of silanol remains. A glassbody obtained exclusively from tetraalkoxysilane has high hardness andhigh light resistance, but a large amount of silanol remains because amolecular chain has a low degree of freedom due to its high degree ofcrosslinking and thus no complete condensation occurs. Also, when ahydrolyzed/condensed liquid is dried and cured, thickening is swift dueto a large number of crosslinking points and the drying and curingproceed simultaneously, resulting in a bulk body with a largedistortion. If such a member is used as a semiconductor device memberfor a long period of time, new internal stress is likely to arise due tocondensation of the residual silanols, leading to the proneness to suchmalfunctions as cracks, peelings and breakings of wires. Also, in thefractured surface of the member, more silanol is found and thus moistureinfiltration is likely to occur because, though moisture permeability islow, its surface hygroscopicity is high. The silanol content can bereduced by high-temperature firing at 400° C. or higher, but it is notpractical because the heat-resistant temperature of most semiconductordevices is 260° C. or lower.

The semiconductor device member of the present invention, on the otherhand, has superior capabilities such as little variation over timebecause it is low in silanol content, superiority in long-termperformance stability, and low hygroscopicity. However, no silanolcontent in a member results only in poor adhesion to the semiconductordevice, and therefore, there is such an appropriate range of the silanolcontent as described above in the present invention.

Since the semiconductor device member of the present invention containsan appropriate amount of silanol, the silanol is bound to a polarportion existing on the device surface through hydrogen bond so that theadhesion develops. The polar portion includes, for example, a hydroxylgroup and an oxygen in a metalloxane bond.

The semiconductor device member of the present invention can form, dueto dehydration condensation, a covalent bond with a hydroxyl group onthe device surface when heated in the presence of an appropriatecatalyst, leading to a development of still firmer adhesion.

If too much content of silanol is contained, on the other hand,thickening in the system, as described above, may make the applicationdifficult, and also, with increased activity, the occurance of curingbefore light-boiling components volatilize by heating may induce afoaming and an increase in internal stress, which may result in a crackgeneration.

The silanol content of a semiconductor device member can be decided bythe method to be described later, for example, using a solid Si-NMRspectrum measurement. Namely, it can be calculated by comparing theratio (%) of silicon atoms in silanol to all silicon atoms, decided fromthe ratio of peak areas originating from silanol to all peak areas, withthe silicon content analyzed separately.

[Solid Si-NMR Spectrum Measurement and Calculation of the SilanolContent]

When measuring the solid Si-NMR spectrum of a semiconductor devicemember, the solid Si-NMR spectrum measurement and the data analysis areperformed first under the following conditions. Then, the ratio (%) ofsilicon atoms in silanol to all silicon atoms is determined from theratio of peak areas originating from silanol to all peak areas and, bycomparing the determined silicon ratio with the silicon content analyzedseparately, the silanol content is calculated.

In this context, the analysis of the measured data (namely, the analysisof the silanol amount) is carried out by a method in which each peak isdivided and extracted by the waveform separation analysis or the likeutilizing, for example, the Gauss function or Lorentz function.

[Example of Device Conditions]

Device: Infinity CMX-400 nuclear magnetic resonance spectroscopemanufactured by Chemagnetics Inc.

²⁹Si resonance frequency: 79.436 MHz

Probe: 7.5 mm φ CP/MAS probe

Temperature: Room temperature

Rotational frequency of sample: 4 kHz

Measurement method: Single pulse method

¹H decoupling frequency: 50 kHz

²⁹Si flip angle: 90°

²⁹Si 90° pulse width: 5.0 μs

Repetition time: 600 s

Total count: 128 times

Observation width: 30 kHz

Broadening factor: 20 Hz

[Example of Data Processing]

For the semiconductor device member, 512 points are taken in as measureddata and zero-filled to 8192 points before Fourier transformation isperformed.

[Example of Waveform Separation Analysis]

For each peak of the spectrum after Fourier transformation, anoptimization calculation is performed by the nonlinear least squaremethod using the center position, height and full width at half maximumof a peak shape that are created by a Lorentz waveform, Gauss waveformor a mixture of both, as variable parameters.

For identification of a peak, refer to AIChE Journal, 44(5), p. 1141,1998, or the like.

The silanol content of a semiconductor device member can also bedetermined by IR measurement described below. In the IR measurement,identification of a silanol peak is not difficult, but the shape of thepeak is broad and thus error in estimating the area is unavoidable.Further, in quantative measurement, it is essential to prepare a sampleof constant thickness accurately, which is a cumbersome work. Foraccurate quantative measurement, therefore, use of solid Si-NMR ispreferable. In measurement based on solid Si-NMR, IR measurement can beused complementarily to determine silanol content in such cases thatsilanol content is too small for detection, or isolation of silanol peakis difficult because of overlapping of several peaks, or chemical shiftof silanol peak is unknown because of an unknown sample.

[Calculation of Silanol Content by IR Measurement]

Fourier Transform Infrared Spectroscopy

Instrument: NEXUS670 and Nic-Plan (Manufactured by Thermo Electron)

Limit of resolution: 4 cm⁻¹

Total count: 64 times

Purge: N₂

Example of measurement: A thin-film sample of 200 μm in thickness isapplied on an Si wafer, and an infrared absorption spectrum is measuredby the transmission method together with the Si wafer. The total area ofsilanol peaks at wave numbers of 3751 cm⁻¹ and 3701 cm⁻¹ is determined.A trimethylsilanol, as a sample of known concentration, is diluted withanhydrous carbon tetrachloride and its infrared absorption spectrum ismeasured by the transmission method using a liquid cell of 200 μm inlight path, and the peak area is compared with that of the actual sampleto obtain the silanol concentration of the actual sample. Since a peakdue to water adsorbed on the sample appears in the background of thesilanol peak in the infrared absorption spectrum, the thin-film sampleshould be heated at 150° C. for 20 minutes or longer at normal pressureor at 100° C. for 10 minutes or longer in vacuo to remove the adsorbedwater before measurement.

[Ratio Between Total Amounts of Silanol Content and Alkoxy GroupContent]

Regarding each total amount of silanol content and alkoxy group contentin the semiconductor device member of the present invention, the amountof silanol is preferably equal to or larger than that of alkoxy group inmolar ratio. In theory, silanol and alkoxy group react to form methanoland siloxane bond with equivalent molar ratios to each other. Therefore,a silanol amount that is equal to or more of the alkoxy group amount canproceed with the curing and condensation just by heat, namely, withoutmoisture supply form the air. In such a case, the semiconductor devicemember is superior in hardenability at the deep portion, even whenapplied in a deep package.

An amount of silanol, in large excess of the amount of alkoxy group,improves reactivity of adhesion to the surface of the semiconductordevice, because of a heightened reaction activity of the semiconductordevice member. This further enables inhibition of poor curing due toremaining alkoxy group, which has low chemical reactivity, and reductionin deformation, shrinkage and weight loss during a high-temperaturestorage. This is why, the ratio represented by {the number of alkoxygroups/(the number of silanols+the number of alkoxy groups)}×100(namely, the proportion of the alkoxy groups in the unreacted ends thatcan be subjected to dehydration and dealcoholization condensation) isusually 0% or larger, and usually 50% or smaller, preferably 30% orsmaller, and particularly preferably 25% or smaller. This ratio can bedecided from a measurement value of liquid-state ²⁹Si-NMR.

In order for the ratio to fall within the above-mentioned range, forexample, the material alkoxysilane should be hydrolyzed sufficiently,the alcohol formed should be distilled off out of the system securely,and as little alcohol as possible should be used as solvent, in thesynthesis process. Or otherwise, for preparing asemiconductor-device-member formation liquid that is superior in storagestability even when containing a large amount of silanol ends,components having a structural unit (B) below should be used as rawmaterials more in molar ratio than the components having a structuralunit (A) below, for example.

(R¹SiO_(1.5))  (A)

(In the formula (A), R¹ represents an organic group.)

((R²)₂SiO)  (B)

(In the formula (B), R²s represent organic groups, independently of eachother.)

The method for measuring liquid-state ²⁹Si-NMR spectrum is as follows.

[Method for Measuring Liquid-State ²⁹Si-NMR Spectrum]

The measurement and data analysis of the liquid-state ²⁹Si-NMR spectrumis carried out under the following conditions.

[Example of Sample Conditions]

50 g of heavy acetone, 2.5 g of tetramethylsilane and 1.5 g of chromiumacetylacetonate as relaxation reagent are mixed. This mixture will bereferred to as “X liquid”.

3.0 g of measurement sample, 0.5 g of the above-mentioned X liquid and1.0 g of heavy acetone are mixed. The whole of them are thrown into a10-mm sample tube made of Teflon (registered trademark) for measurement.

A two-pack type commercially available silicone resin, for example, isunmeasurable after they are blended because it is thickened during themeasurement. NMR measurements are then performed for each of the baseresin and the curing agent separately before they are mixed, and thedata is calculated assuming that the spectrum after mixing will be thequantity sum of each single spectrum with consideration for the mixingratio. The influences of errors at each measurement are removed frompeak intensities of the base resin and the curing agent respectively, bynormalization with the area of the internal standard tetramethylsilanetaken as 1.

[Example of Device Conditions]

Device: JNM-AL400 nuclear magnetic resonance spectroscope manufacturedby JEOL Ltd.

²⁹Si resonance frequency: 78.50 MHz

Probe: AT 10 probe

Measurement temperature: 25.0° C.

Rotational frequency of sample: no rotation

Measurement method: Single pulse method

Pulse delay time: 12.7 s

Total count: 512 times

Broadening factor: 1.0 Hz

[Example of Waveform Processing Analysis]

For each peak of the spectrum after Fourier transform, the chemicalshift is decided from each peak top position and the integration isperformed. For identification of a peak, refer to AIChE Journal, 44(5),p. 1141, 1998, or the like.

For example when a peak of hydrosilyl group silicon originating from(—Si—O—)₂CH₃SiH is detected from −30 ppm to −40 ppm in an analysis ofcommercially available silicone resin, this peak is categorized asbifunctional silicon.

[1-4-3] UV Transmittance

The semiconductor device member of the present invention preferably haslight transmittance, with respect to the luminous wavelength of asemiconductor light-emitting device, of usually 80% or more, amongothers 85% or more, and further 90% or more, when used for asemiconductor light-emitting device and having a film thickness of 1.0mm. The efficiency of extracting light in the semiconductorlight-emitting device has been enhanced by various technologies.However, if the transparency of a translucent member for sealing asemiconductor element or holding a phosphor is low, the brightness of asemiconductor light-emitting device using the translucent member will bereduced, making it difficult to obtain a high-brightness semiconductorlight-emitting device product.

In this context, a “luminous wavelength of a semiconductorlight-emitting device” varies depending on the type of semiconductorlight-emitting device, but it generally refers to wavelengths in a rangeof usually 300 nm or longer, preferably 350 nm or longer, and usually900 nm or shorter, preferably 500 nm or shorter. If the lighttransmittance is low with respect to the wavelengths in this range, thesemiconductor device member absorbs the light and the efficiency ofextracting light decreases, making it impossible to obtain ahigh-brightness semiconductor light-emitting device. Further, such a lowlight transmittance is undesirable because energy for the reducedefficiency of extracting light is converted into heat, leading to thethermal degradation of the semiconductor light-emitting device.

Incidentally, sealing members tend to degrade due to light of whichwavelength is in the ultraviolet to blue region (300 nm to 500 nm).Therefore, the semiconductor device member of the present invention,which is superior in durability, can be preferably used for asemiconductor light-emitting device having its luminous wavelength inthis region for achieving a considerably advantageous effect.

Light transmittance of a semiconductor device member can be measuredwith an ultraviolet spectrophotometer by, for example, a techniquedescribed below, using a sample of singly cured film with a smoothsurface having a thickness of 1 mm.

[Measurement of Transmittance]

Transmittance is measured using a singly cured film of a semiconductordevice member of about 1 mm in thickness with a smooth surface andwithout defects or unevenness that may cause scatterings, using anultraviolet spectrophotometer (UV-3100, manufactured by ShimadzuCorporation) in the wavelength range of 200 nm to 800 nm.

The shape of the semiconductor light-emitting device is diverse, butmostly it is used in a thick-film state having thickness exceeding 0.1mm. However, it is sometimes used as a thin film, in such cases asproviding a thin-film phosphor layer (for example, a layer containingnanometer-size phosphor particles or fluorescent ions, having thicknessof several μm) at the position apart from the LED chip (luminouselement) or providing a high refractive-index light extracting film on athin film right above the LED chip. In such cases, it is preferable thatthe transmittance of the film with this thickness is 80% or more. Evenwhen applied to such a thin-film, the semiconductor device member of thepresent invention shows superiority in light resistance, heat resistanceand sealing properties, as well as capability of being formed into afilm steadily without generating cracks or the like.

[1-4-4 Peak Area Ratio]

The semiconductor device member of the present invention preferablysatisfies the following condition. That is, in the semiconductor devicemember of the present invention, the ratio of (total area of peaks ofthe chemical shift of −40 ppm or more and 0 ppm or less)/(total area ofpeaks of the chemical shift of less than −40 ppm) in a solid Si-nuclearmagnetic resonance spectrum (hereinafter referred to as “peak area ratioaccording to the present invention” when appropriate) is usually 3 ormore, preferably 5 or more, and still preferably 10 or more, and usually200 or less, preferably 100 or less, and still preferably 50 or less.

That the peak area ratio according to the present invention is withinthe above range means that the semiconductor device member of thepresent invention has more bifunctional silane than silanes oftrifunctional or more, such as trifunctional silane and tetrafunctionalsilane. With more bifunctional silanes being provided, as describedabove, the semiconductor device member of the present invention canpresent elastomer properties and thus the stress can be relieved.

However, the semiconductor device member of the present invention maypresent elastomer properties even without satisfying the above-mentionedcondition of the peak area ratio according to the present invention.This is a case when, for example, the semiconductor device member of thepresent invention is produced by using a coupling agent such as alkoxideof metal excluding silicon as a crosslinking agent. The technique usedfor making the semiconductor device member of the present inventionpresent elastomer properties is arbitrary and is not limited to theabove-mentioned condition with respect to the peak area ratio accordingto the present invention.

[1-4-5] Functional Group

The semiconductor device member of the present invention comprises afunctional group capable of forming a hydrogen bond with a predeterminedfunctional group (for example, a hydroxyl group or an oxygen in ametalloxane bond) that is present on the surface of a resin likepolyphthalamide, ceramic or a metal. A container (such as a cupdescribed later, hereinafter referred to as “container of semiconductordevice” as appropriate) for a semiconductor device is usually formed ofa ceramic or a metal. Also, a hydroxyl group usually exists on thesurface of a ceramic and a metal. On the other hand, the semiconductordevice member of the present invention usually comprises a functionalgroup capable of forming a hydrogen bond with that hydroxyl group.Therefore, the semiconductor device member of the present invention issuperior in adhesion to the containers of semiconductor devices due tothe above-mentioned hydrogen bond.

Functional groups of the semiconductor device member of the presentinvention that can be bound to the hydroxyl group through hydrogen bondinclude, for example, silanol, alkoxy group, amino group, imino group,methacryl group, acryl group, thiol group, epoxy group, ether group,carbonyl group, carboxyl group and sulfonate group. Of these, silanol,and alkoxy group are preferable, from the standpoint of heat resistance.At this point, only one functional group or two or more types offunctional groups may be used.

Whether the semiconductor device member of the present invention has anyfunctional group that can be bound to the hydroxyl group throughhydrogen bond, as described above, can be checked by a technique ofspectroscopy such as solid Si-NMR, solid ¹H-NMR, infrared absorptionspectrum (IR) and Raman spectrum.

[1-4-6] Heat Resistance

The semiconductor device member of the present invention is superior inheat resistance. That is, the semiconductor device member of the presentinvention has a property that transmittance thereof with respect tolight having a predetermined wavelength hardly varies even when leftunder a high temperature condition. More specifically, the maintenancerate of transmittance of the semiconductor device member of the presentinvention with respect to the light having a wavelength of 400 nm beforeand after being kept for 500 hours at temperature of 200° C. is usually80% or more, preferably 90% or more, and more preferably 95% or more,and usually 110% or less, preferably 105% or less, and more preferably100% less.

The above ratio of variation can be measured in the same way as themethod of measuring the transmittance, described earlier in [1-4-3], bymeans of measuring transmittance using an ultraviolet/visiblespectrophotometer.

[1-4-7] UV Resistance

The semiconductor device member of the present invention is superior inlight resistance. That is, the semiconductor device member of thepresent invention has a property that transmittance thereof with respectto the light having a predetermined wavelength hardly varies even whenirradiated with UV (ultraviolet light). More specifically, themaintenance rate of transmittance with respect to light of 400-nmwavelength of the semiconductor device member of the present inventionbefore and after being irradiated with light whose center wavelength is380 nm and radiant intensity is 0.4 kW/m² (sic) for 72 hours is usually80% or more, preferably 90% or more, and more preferably 95% or more,and usually 110% or less, preferably 105% or less, and more preferably100% or less.

The above ratio of variation can be measured in the same way as themethod of measuring the transmittance, described earlier in [1-4-3], bymeans of measuring transmittance using an ultraviolet/visiblespectrophotometer.

[1-4-8] Residual Amount of Catalyst

The semiconductor device member of the present invention is usuallyproduced using an organometallic compound catalyst containing at leastone kind of element selected from zirconium, hafnium, tin, zinc andtitanium. Therefore, usually in the semiconductor device member of thepresent invention, these catalysts are remained. Specifically, thesemiconductor device member of the present invention contains theabove-mentioned organometallic compound catalysts in the amount ofusually 0.001 weight % or more, preferably 0.01 weight % or more, morepreferably 0.02 weight % or more, and usually 0.3 weight % or less,preferably 0.2 weight % or less, more preferably 0.1 weight % or less,in terms of metal element.

The above-mentioned content of the organometallic compound catalyst canbe measured by ICP analysis.

[1-4-9] Low-Boiling Component

It is preferable for the semiconductor device member of the presentinvention that the integrated area of chromatogram, in TG-mass(pyrolysis-mass spectrometry chromatogram), of the gas generated byheating at the temperature from 40° C. to 210° C. is small.

TG-mass detects low-boiling components in a semiconductor device memberby heating the semiconductor device member. A large integrated area ofchromatogram in the range from 40° C. to 210° C. indicates thatlow-boiling components such as water, solvent and three-membered tofive-membered cyclic siloxane are present in the component. In such acase, there are such possibilities that (i) the large amount oflow-boiling components induces occurrence of air bubbles or bleedout inthe curing process, thereby lowering the adhesion to the container ofsemiconductor device, and (ii) a heat generated during use inducesoccurrence of air bubbles or bleedout. Therefore, it is preferable forthe semiconductor device member of the present invention to contain lesslow-boiling components.

As methods can be cited the followings, for example, by which the amountof above-mentioned low-boiling components, which can be detected byTG-mass, is reduced in the semiconductor device member of the presentinvention.

(i) Inhibiting the low-molecular weight materials from remaining bycarrying out polymerization reaction or the like sufficiently. Forexample when a polycondensate prepared by a hydrolysis andpolycondensation reaction of a specific compound, such as in “[2]Production method of semiconductor device member” to be described later,is used as the semiconductor device member of the present invention, thehydrolysis and polycondensation is performed under normal pressureusually at 15° C. or higher, preferably at 20° C. or higher, morepreferably at 40° C. or higher, and usually at 140° C. or lower,preferably at 135° C. or lower, more preferably at 130° C. or lower. Thereaction time of the hydrolysis and polycondensation depends on thereaction temperature. But the reaction proceeds over a period of usually0.1 hour or longer, preferably 1 hour or longer, more preferably 3 hoursor longer, and usually 100 hours or shorter, preferably 20 hours orshorter, more preferably 15 hours or shorter. It is preferable that thereaction time is adjusted as appropriate successively with carrying outa molecular weight control by means of GPC or viscosity measurement.Furthermore, the reaction time is preferably adjusted in considerationof the heating-up period.(ii) Removing the low-boiling components efficiently in processes otherthan the polymerization reaction or the like. For example when apolycondensate prepared by a hydrolysis and polycondensation reaction ofa specific compound, such as in “[2] Production method of semiconductordevice member” to be described later, is used as the semiconductordevice member of the present invention, the low-boiling components areremoved in processes of solvent distillation and drying after thepolycondensation reaction process, preventing the polycondensationreaction from proceeding. Specifically, the temperature condition fordistilling off the solvent is set at usually 60° C. or higher,preferably 80° C. or higher, and more preferably 100° C. or higher, andusually 150° C. or lower, preferably 130° C. or lower, and morepreferably 120° C. or lower, for example. In addition, the pressurecondition for the solvent distillation is set usually at normalpressure. Further, the pressure is reduced when necessary so that theboiling point of the reaction liquid during the solvent distillationshould not reach the curing start temperature (usually 120° C. orhigher). Moreover, the processes of solvent distillation and drying arecarried out in an inert gas atmosphere, such as argon gas, nitrogen gasand helium gas.[1-4-10] Combined Use with Other Members

The semiconductor device member of the present invention may be used asa sealant singly. However, it may also be used together with anothermember for more complete cutoff of oxygen or moisture for example whenit seals an organic phosphor, a phosphor that is liable to deteriorateby oxygen or moisture, a semiconductor light-emitting device or thelike. In such a case, an air-tight sealing, using such a highlyair-tight sealant as glass plate or epoxy resin, or vacuum sealing maybe added from outside of the semiconductor device member of the presentinvention, which is provided for retention of the phosphor, sealing thesemiconductor element or extracting light. In this case, the shape ofthe device is not specially limited. Namely, it is enough for thesealant, coating or coated layer, made of the semiconductor devicemember of the present invention, to be substantially protected andblocked from outside by an air-tight material such as metal, glass orhighly air-tight resin, so as to allow no passage of oxygen andmoisture.

In addition, the semiconductor device member of the present inventionmay be used as adhesive agent for a semiconductor light-emitting devicebecause it excels in adhesion as described above. More specifically, forexample, the semiconductor device member of the present invention can beused for bonding a semiconductor element and a package, a semiconductorelement and a sub mount, package constituents together, a semiconductorlight-emitting device and an external optical element, by means ofapplication, printing or potting. Since the semiconductor device memberof the present invention excels particularly in light resistance andheat resistance, it provides a semiconductor light-emitting device withhigh reliability enough to stand a long-time use, when it is used asadhesive agent for a high-power semiconductor light-emitting device thatis exposed to high temperature or ultraviolet rays for a long time.

The semiconductor device member of the present invention can achievesufficient adhesion just by itself. However, for more sufficientadhesion, various surface treatments for improving adhesion may beperformed on the surface that will be directly in contact with thesemiconductor device member. Examples of such surface treatment include:a formation of an adhesion-improving layer using a primer or a silanecoupling agent, a chemical surface treatment using such an agent asacids or bases, a physical surface treatment using plasma irradiation,ion irradiation or electron beam irradiation, a surface-rougheningprocedure by sandblasting, etching or microparticles coating. Otherexamples of the surface treatment for improving adhesion include knownsurface treatment methods such as described in Japanese Patent Laid-OpenPublication (Kokai) No. Hei 5-25300, “Hyomen Kagaku”, Vol. 18 No. 9, pp21-26, written by Norihiro Inagaki, and “Hyomen Kagaku”, Vol. 19 No. 2,pp 44-51 (1998), written by Kazuo Kurosaki.

[1-4-11] Others

There is no limitation on the shape and the dimension of thesemiconductor device member of the present invention, and they can bedecided arbitrarily. For example when the semiconductor device member isused as a sealant with which the inside of a certain container of asemiconductor device is filled, the shape and the dimension of thesemiconductor device member of the present invention are decidedaccording to the shape and the dimension of the container of thesemiconductor device. On the other hand, when the semiconductor devicemember is formed on the surface of a certain substrate, it is oftenformed into a film shape, and the dimension thereof is set arbitrarilydepending on its use.

However, one of the advantageous effects of the semiconductor devicemember of the present invention is that it can be formed into a thickfilm when it is formed into a film shape. Conventional semiconductordevice members are difficult in forming them into thick films, due tooccurrence of cracks or the like caused by an internal stress or thelike. However, there are no such problems in the semiconductor devicemember of the present invention, and it can be formed into a thick filmsteadily. Regarding its specific range, it is preferable for thesemiconductor device member of the present invention to be formed withthickness of usually 0.1 μm or larger, preferably 10 μm or larger, andmore preferably 100 μm or larger. There is no limitation on the upperlimit thereof, but it is usually 10 mm or smaller, preferably 5 mm orsmaller, and more preferably 1 mm or smaller. In this context, when thethickness of the film is not uniform, “thickness of the film” indicatesthe thickness of the film at its thickest portion.

In addition, the semiconductor device member of the present inventioncan usually seal a semiconductor device for a longer period of time thanconventional ones without generating cracks or peelings. Morespecifically, when a semiconductor light-emitting device, sealed withthe semiconductor device member of the present invention, is illuminatedin a continuous manner at 85-° C. temperature and 85-% relative humiditywith usually 20 mA or more, preferably 350 mA or more of drivingcurrent, the brightness after usually 500 hours or longer, preferably1000 hours or longer, more preferably 2000 hours or longer of theillumination relative to that of just after switched on is notdecreased.

The semiconductor device member may contain another component, dependingon its use. For example when the semiconductor device member of thepresent invention is used as a constituent of a semiconductorlight-emitting device, it may contain a phosphor, inorganic particle orthe like. Explanation will be given on this point later, together withan explanation on the use of the member.

The other components may be used either as a single kind thereof or as amixture of two or more kinds in any combination and in any ratio.

In addition, a minute amount of alkoxy group usually remains in thesemiconductor device member of the present invention. A semiconductordevice member containing less of this terminal alkoxy group shows smallweight loss, measured with TG-DTA, leading to high heat resistance.

[2] Production Method of Semiconductor Device Member

The production method of the semiconductor device member of the presentinvention is not particularly limited. It can be produced, for example,by performing hydrolysis and polycondensation of a compound representedby the general formula (1) or (2) shown below and/or its oligomer anddrying the obtained polycondensate (hydrolyzate/polycondensate).However, since it is preferable for the semiconductor device member ofthe present invention to consist of siloxane bonds as its main body, acompound represented by the general formula (1) or its oligomer ispreferably used as the main material. When thehydrolyzate/polycondensate contains a solvent, the solvent may bedistilled off in advance before the drying process.

In the following explanation, the above-mentionedhydrolyzate/polycondensate or a composite containing it, which isobtained before the drying process, is referred to as“semiconductor-device-member formation liquid”. Accordingly, when asemiconductor device member of the present invention is produced by theproduction method described in this section (hereinafter referred to as“production method of the present invention” as appropriate), thesemiconductor device member will be obtained by drying thesemiconductor-device-member formation liquid. The production method ofthe semiconductor device member will be described below in detail.

[2-1] Material

A compound represented by the general formula (1) shown below(hereinafter called “compound (1)” when appropriate) and/or its oligomerare used as material.

[Chemical Formula 3]

M^(m+)X_(n)Y¹ _(m−n)  (1)

In the general formula (1), M represents at least one element selectedfrom the group consisting of silicon, aluminum, zirconium and titanium.Of these, silicon is preferable.

In the general formula (1), m represents the valence of M and is aninteger of 1 or larger and 4 or smaller. In addition, “m+” indicatesthat it is a positive valence.

n represents the number of X groups and is an integer of 1 or greaterand 4 or smaller. However, m≧n holds.

In the general formula (1), X is a hydrolyzable group that generates ahighly reactive hydroxyl group after being hydrolyzed by water in thesolution, moisture in the air or the like. As X, any conventionallyknown one can arbitrarily be used. For example, a low-grade alkoxy groupof C1 to C5, acetoxy group, butanoxy group and chlorine group can becited. In this context, the expression of Ci (i is an integer) indicatesthat the number of carbon atoms is i. Furthermore, X may be a hydroxylgroup. One hydrolyzable group may be used alone or two or morehydrolyzable groups may be used together in any combination at anyratio.

Of these, the low-grade alkoxy group of C1 to C5 is preferable, sincecomponent liberated after the reaction is neutral. Particularly, methoxygroup or ethoxy group is preferable because these groups are highlyreactive and the liberated solvent is low-boiling.

Further, when X in the general formula (1) is an acetoxy group orchlorine group and insulating property is needed for the semiconductordevice member, it is preferable to add a process of removing acidcomponents, because acetic acid or hydrochloric acid is then liberatedafter the hydrolysis reaction.

As Y¹ in the general formula (1), any known monovalent organic group ofthe so-called silane coupling agent can arbitrarily be selected andused. Among others, an organic group particularly useful as Y¹ in thegeneral formula (1) in the present invention can be selected from thegroup Y⁰ (group of useful organic groups) shown below. Another organicgroup can also be selected as appropriate, for the purpose of improvingthe affinity to other materials constituting the semiconductor device,improving the adhesion, adjusting the refractive index of thesemiconductor device member and the like.

<Group of Useful Organic Groups Y⁰>

Y⁰: Monovalent or higher organic groups derived from aliphaticcompounds, alicyclic compounds, aromatic compounds andaliphatic-aromatic compounds.

The number of carbon atoms of the organic groups belonging to the groupY⁰ is usually 1 or more, and usually 1000 or less, preferably 500 orless, more preferably 100 or less, and still more preferably 50 or less.

Further, at least a part of hydrogen atoms in the organic groupbelonging to the group Y⁰ may be substituted by atoms and/orsubstituents such as organic functional groups exemplified below. Inthis case, a plurality of hydrogen atoms in the organic group belongingto the group Y⁰ may be substituted by the following substituents. Insuch a case, a combination of one kind of substituent or two or morekinds of substituents, selected from the substituents shown below, maybe used for the substitution.

Examples of substituents that can be substituted for the hydrogen atomin the organic groups belonging to the group Y⁰ include: atoms such asF, Cl, Br and I; and organic functional groups such as vinyl group,methacryloxy group, acryloxy group, styryl group, mercapto group, epoxygroup, epoxy cyclohexyl group, glycidoxy group, amino group, cyanogroup, nitro group, sulfonic acid group, carboxy group, hydroxy group,acyl group, alkoxy group, imino group and phenyl group.

Among substituents that can be substituted for the hydrogen atom in theorganic groups belonging to the group Y⁰, the organic functional groupsmay have a substituent of a halogen atom, such as F, Cl, Br and I, forat least a part of hydrogen atoms in the organic functional groups, inall the cases described above.

Among the substituents exemplified above as substitutable for thehydrogen in the organic groups belonging to the group Y⁰, theabove-listed organic functional groups are examples that can beintroduced easily. Therefore, another organic functional group havingvarious physicochemical functionalities may be introduced in accordancewith the purposes of use.

In addition, organic groups belonging to the group Y⁰ may also havetherein various atoms such as O, N and S or atomic groups as connectinggroups.

As Y¹ in the general formula (1), various groups can be selected, forexample from the organic groups belonging to the above group of usefulorganic groups Y⁰, in accordance with the purposes. However, in terms ofsuperiority in UV resistance and heat resistance, it is preferable forY¹ to consist mainly of methyl group.

Concrete examples of the above compound (1) where M is silicon include:dimethyldimethoxysilane, dimethyldiethoxysilane,diphenyldimethoxysilane, diphenyldiethoxysilane, vinyl trimethoxysilane,vinyl triethoxysilane, vinyl triacethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxy cyclohexyl)ethyltrimethoxysilane,γ-(3,4-epoxy cyclohexyl)ethyltriethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, phenyl trimethoxysilane, phenyl triacethoxysilane,γ-mercaptopropyl trimethoxysilane, γ-chloropropyl trimethoxysilane,β-cyanoethyl triethoxysilane, methyltrimethoxysilane,methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane,ethyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane,tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane,dimethyldichlorosilane, diphenyldichlorosilane, methylphenyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane,trimethylchlorosilane, methyltrichlorosilane, γ-asinopropyltriethoxysilane (sic), 4-asinobutyl triethoxysilane (sic), p-aminophenyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane,aminoethyl aminomethylphenethyl trimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxy cyclohexyl)ethyltrimethoxysilane,3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane,4-aminobutyl triethoxysilane, N-(6-aminohexyl)aminopropyltrimethoxysilane, 3-chloropropyl trimethoxysilane,3-chloropropyltrichlorosilane, (p-chloromethyl)phenyltrimethoxysilane,4-chlorophenyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane,3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl trimethoxysilane,styrylethyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, vinyltrichlorosilane, vinyl tris (2-methoxyethoxy)silane, and trifluoropropyltrimethoxysilane.

Concrete examples of the compounds (1) where M is aluminum include:aluminum triisopropoxide, aluminum tri-n-butoxide, aluminumtri-t-butoxide, and aluminum triethoxide.

Concrete examples of the compounds (1) where M is zirconium include:zirconium tetramethoxide, zirconium tetraethoxide, zirconiumtetra-n-propoxide, zirconium tetra-i-propoxide, zirconiumtetra-n-butoxide, zirconium tetra-i-butoxide, zirconiumtetra-t-butoxide, and zirconium dimethacrylate dibutoxide.

Concrete examples of the compounds (1) where M is titanium include:titanium tetraisopropoxide, titanium tetra-n-butoxide, titaniumtetra-i-butoxide, titanium methacrylate triisopropoxide, titaniumtetramethoxypropoxide, titanium tetra-n-propoxide, and titaniumtetraethoxide.

However, these compounds exemplified above are only a part of couplingagents easily available on the market. More detailed list thereof can beshown, for example, by the list of coupling agents and the relatedproducts in Chapter 9 of “Coupling-Zai Saiteki Riyo Gijutsu” issued byInstitute for Science and Technology. Of course, the coupling agentsthat can be used for the present invention are not limited to theseexamples.

A compound represented by the general formula (2) below (hereinaftercalled “compound (2)” when appropriate) and/or its oligomer can also beused in the same manner as the above-mentioned compound (1) and/or itsoligomer.

[Chemical Formula 4]

(M^(s+)X_(t)Y¹ _(s−t−1))_(u)Y²  (2)

In the general formula (2), M, X, and Y¹ represent, independently ofeach other, the same things as those in the general formula (1).Particularly as Y¹, in the same way as the general formula (1), variousgroups can be selected, for example from the organic groups belonging tothe above-mentioned group of useful organic groups Y⁰ in accordance withthe purposes. However, in terms of superiority in UV resistance and heatresistance, it is preferable for Y¹ to consist mainly of methyl group.

In the general formula (2), s represents the valence of M and is aninteger of 2 or larger and 4 or smaller. In addition, “s+” indicatesthat it is a positive valence.

Further, in the general formula (2), Y² represents a u-valent organicgroup. At this point, represents an integer of 2 or larger. As Y² in thegeneral formula (2), any known bivalent or higher organic group of theso-called silane coupling agent can arbitrarily be selected and used.

Also, in the general formula (2), t represents an integer of 1 or largerand s−1 or smaller, where t≦s.

Examples of the above-mentioned compound (2) include: various organicpolymers and oligomers to which a plurality of hydrolytic silyl groupsare bound as side chains, siloxane polymers to which a hydrolytic silylgroup is bound through an organic connecting group such as methylenechain, and molecules to which hydrolytic silyl groups are bound at theposition of plural ends of the molecules.

Concrete examples of the above compound (2) and its product names arelisted below:

-   Bis(triethoxysilylpropyl)tetrasulfide

(Manufactured by Shin-Etsu Chemical Co., Ltd., KBE-846)

-   2-diethoxymethyl ethylsilyldimethyl-2-furanylsilane

(Manufactured by Shin-Etsu Chemical Co., Ltd., LS-7740)

-   N,N′-bis[3-(trimethoxysilyl)propyl]ethylenediamine

(Manufactured by Chisso Corporation, Sila-Ace XS1003)

-   N-glycidyl-N,N-bis[3-(methyldimethoxysilyl)propyl]amine

(Manufactured by Toshiba Silicones Co., Ltd., TSL8227)

-   N-glycidyl-N,N-bis[3-(trimethoxysilyl)propyl]amine

(Manufactured by Toshiba Silicones Co., Ltd., TSL8228)

-   N,N-bis[(methyldimethoxysilyl)propyl]amine

(Manufactured by Toshiba Silicones Co., Ltd., TSL8206)

-   N,N-bis[3-(methyldimethoxysilyl)propyl]ethylenediamine

(Manufactured by Toshiba Silicones Co., Ltd., TSL8212)

-   N,N-bis[(methyldimethoxysilyl)propyl]methacrylamide

(Manufactured by Toshiba Silicones Co., Ltd., TSL8213)

-   N,N-bis[3-(trimethoxysilyl)propyl]amine

(Manufactured by Toshiba Silicones Co., Ltd., TSL8208)

-   N,N-bis[3-trimethoxysilyl)propyl]ethylenediamine

(Manufactured by Toshiba Silicones Co., Ltd., TSL8214)

-   N,N-bis[3-(trimethoxysilyl)propyl]methacrylamide

(Manufactured by Toshiba Silicones Co., Ltd., TSL8215)

-   N,N′,N″-tris[3-(trimethoxysilyl)propyl]isocyanurate

(Manufactured by Hydrus Chemical Inc., 12267-1)

-   1,4-bis hydroxy dimethylsilyl benzene

(Manufactured by Shin-Etsu Chemical Co., Ltd., LS-7325)

The compound (2) can also be synthesized by a hitherto known synthesismethod other than hydrolysis and polycondensation. For example, ahydrolyzable silyl group can be introduced by addition condensation ofalkoxysilane containing vinyl group to a polydimethylsiloxane chainhaving SiH group via hydrosilylation reaction. Or otherwise, ahydrolyzable silyl group can be introduced by copolymerization of vinyltrialkoxysilane with acrylic monomer or vinyl monomer. In such cases,unreacted residue originating from the synthesis of compound (2) orcatalyst may remain in the system. However, it is preferable that theamount of such unreacted residue or catalyst is reduced to the degreethat the semiconductor device member can maintain its performance.Specifically, it is preferable to use a fixed catalyst and remove itafter the reaction, or to keep the catalyst concentration as low aspossible enough for the reaction to proceed.

As the material, compound (1), compound (2), and/or their oligomers canbe used. That is, in the production method of the present invention,compound (1), oligomer of the compound (1), compound (2), oligomer ofthe compound (2), or oligomer of the compound (1) and compound (2) maybe used as the material. If oligomer of compound (1) or oligomer ofcompound (2) is used as the material, the molecular weight of theoligomer is arbitrary as long as the semiconductor device member of thepresent invention can be obtained. However, it is usually 400 or larger.

If compound (2) and/or oligomer thereof are used as main material, amain chain structure in the system will consist principally of organicbonds, leading possibly to a low durability. Thus, it is desirable touse a minimum amount of compound (2) in order to provide mainlyfunctionality such as adhesion addition, refractive index adjustment,reactivity control, and inorganic-particles dispersibility addition. Ifcompound (1) and/or its oligomer (compound-(1) derived component) andcompound (2) and/or its oligomer (compound-(2) derived component) areused simultaneously, it is desirable that the ratio of usage ofcompound-(2) derived component to the total weight of the material isusually 30 weight % or less, preferably 20 weight % or less, and morepreferably 10 weight % or less.

If, in the production method of the semiconductor-device-memberformation liquid and the semiconductor device member of the presentinvention, an oligomer of compound (1) or compound (2) is used asmaterial, the oligomer may be prepared in advance, but it may also beprepared during the production process. That is, it is possible to use amonomer such as compound (1) or compound (2) as material in order toform an oligomer during the production process before the subsequentreactions are allowed to proceed using the oligomer.

As oligomer, the one having, as a result, a similar structure to theoligomer that can be obtained from a monomer such as compound (1) orcompound (2) can be used. A commercially available oligomer having sucha structure can also be used. Concrete examples of such an oligomerinclude the following ones.

<Example of Oligomers Consisting Only of Bifunctional Silicon>

Examples of dimethyl polysiloxane with terminal hydroxyl groupmanufactured by GE Toshiba Silicones Co., Ltd. include XC96-723, XF3905,YF3057, YF3800, YF3802, YF3807 and YF3897.

Examples of methylphenyl polysiloxane with terminal hydroxyl groupmanufactured by GE Toshiba Silicones Co., Ltd. include YF3804.

Examples of double-ended silanol polydimethylsiloxane manufactured byGelest Inc. include DMS-S12 and DMS-S14.

Examples of double-ended silanol diphenylsiloxane-dimethylsiloxanecopolymer manufactured by Gelest Inc. include PDS-1615.

Examples of double-ended silanol polydiphenylsiloxane manufactured byGelest Inc. include PDS-9931.

<Example of Oligomers Containing Trifunctional or More of Silicon>

Examples of silicone alkoxy oligomer (methyl/methoxy type) manufacturedby Shin-Etsu Chemical Co., Ltd. include KC-89S, KR-500, X-40-9225,X-40-9246 and X-40-9250.

Examples of silicone alkoxy oligomer (phenyl/methoxy type) manufacturedby Shin-Etsu Chemical Co., Ltd. include KR-217.

Examples of silicone alkoxy oligomer (methylphenyl/methoxy type)manufactured by Shin-Etsu Chemical Co., Ltd. include KR-9218, KR-213,KR-510, X-40-9227 and X-40-9247.

Of these, oligomers consisting only of bifunctional silicon areinstrumental in giving plasticity to the semiconductor device member ofthe present invention, but the mechanical strength of the member tendsto be insufficient. Therefore, through copolymerization with an monomercomprising trifunctional or more of silicon or with an oligomercontaining trifunctional or more of silicon, the semiconductor devicemember of the present invention can be equipped with a mechanicalstrength necessary as sealant. In addition, those having silanol asreactive group need not be hydrolyzed beforehand and are advantageous inthat the use of such solvent as alcohol as water miscible solvent is notnecessary. When oligomers having alkoxy group are used as material,water for effecting hydrolysis is needed, as is the case of monomershaving alkoxy group.

Further, as the material, any single one of compound (1), compound (2)and their oligomers may be used, or otherwise, two or more of them maybe mixed to be used in an arbitrary combination and composition.Further, compound (1), compound (2) and their oligomers that arehydrolyzed in advance (namely, X in general formulas (1) and (2) is OHgroup) may also be used.

However, in the present invention, at least one of compound (1),compound (2) and their oligomers (including those hydrolyzed),containing silicon as M and having at least one of the organic group Y¹and organic group Y², is necessary to be used. Since it is preferablethat crosslinkings in the system are formed mainly by inorganiccomponents including siloxane bond, when both compound (1) and compound(2) are used, it is preferable that compound (1) is mainly used.

To obtain a semiconductor device member consisting principally ofsiloxane bond, compound (1) and/or an oligomer thereof are preferablyused as main component of the material. Further, it is more preferablethat the oligomer of compound (1) and/or the oligomer of compound (2)are mainly composed of bifunctional components. Particularly, thebifunctional unit of the oligomer of compound (1) and/or the oligomer ofcompound (2) are preferably used as bifunctional oligomers.

Further, if the bifunctional component (hereinafter called “bifunctionalcomponent oligomer” when appropriate) of the oligomer of compound (1)and/or the oligomer of compound (2) are mainly used, the ratio of usageof the bifunctional component oligomers to the total weight of thematerial (that is, the sum of the weights of compound (1), compound (2)and their oligomers) is usually 50 weight % or more, preferably 60weight % or more, and more preferably 70 weight % or more. The upperlimit of the above ratio is usually 97 weight %. This is because using abifunctional component oligomer as main component of the material is oneof the factors that make it easy to produce the semiconductor devicemember of the present invention by the production method of thesemiconductor device member of the present invention.

Advantages of using a bifunctional component oligomer as main componentof the material will be described below in detail.

In a semiconductor device member produced by conventional sol gelmethod, the hydrolyzate/polycondensate (including thehydrolyzate/polycondensate contained in the coating liquid (hydrolyzingliquid)) obtained by hydrolysis and polycondensation of the materialshowed high reaction activity. Thus, unless thehydrolyzate/polycondensate was diluted by a solvent such as alcohol,polymerization in the system would proceed rapidly before being cured,making molding and handling difficult. For example, if not diluted by asolvent, the hydrolyzate/polycondensate was sometimes cured even at atemperature around 40° C. to 50° C. Therefore, it was necessary to causea solvent to exist with the hydrolyzate/polycondensate in order toensure handleability of the hydrolyzate/polycondensate obtained afterthe hydrolysis.

If a hydrolyzate/polycondensate is dried and cured with the solventcoexisting with the hydrolyzate/polycondensate, shrinkage caused bydesolvation (desolvation shrinkage) is added to the shrinkage caused bydehydration condensation, during the curing. Accordingly, in aconventional semiconductor device, the cured product tended to havelarge internal stress, and therefore, crack generations, peelings, andbreakings of wires, caused by the internal stress, were more likely tooccur.

Further, if more bifunctional component monomers are used as materialfor the purpose of softening the semiconductor device member in order torelieve the above internal stress, there was a possibility of increasinglow-boiling cyclic material in the polycondensation product. Since thelow-boiling cyclic material is volatilized during the curing, theincrease of low-boiling cyclic material will lead to a lower yield byweight. The low-boiling cyclic material is also volatilized from thecured product, leading possibly to generation of stress. Further, heatresistance of the semiconductor device member that contains a largeamount of low-boiling cyclic material may decrease. For the abovereasons, it has been difficult to produce a semiconductor device memberas a cured product in an elastomer state with good performancesconventionally.

In contrast, in the production method of the semiconductor device memberof the present invention, bifunctional components that are oligomerizedin advance in another system (that is, in a system not involved in thehydrolysis and polycondensation process) and of which low-boilingimpurities without reactive ends are distilled off are used as material.Therefore, even if a large amount of bifunctional component (that is,the above bifunctional component oligomer) is used, low-boilingimpurities thereof will not be volatilized, enabling realization ofimprovement in yield by weight of the cured product and producing acured product in an elastomer state with good performances.

Further, the reaction activity of the hydrolyzate/polycondensate can beinhibited by using a bifunctional component oligomer as main material.This phenomenon can be considered to be caused by a steric hindrance andan electron effect of the hydrolyzate/polycondensate, as well as byreduction in amount of silanol ends due to the use of the bifunctionalcomponent oligomer. Because the reaction activity is inhibited, thehydrolyzate/polycondensate is not cured even without a coexistingsolvent, and thus, the hydrolyzate/polycondensate can be made bothone-component type and a non-solvent system.

Also, because the reaction activity of the hydrolyzate/polycondensate isreduced, the curing start temperature can be set higher than before.Therefore, when a solvent whose temperature is lower than the curingstart temperature of the hydrolyzate/polycondensate coexists, thesolvent will be volatilized before the curing of thehydrolyzate/polycondensate starts in the drying process of thehydrolyzate/polycondensate. This makes it possible to inhibit thegeneration of an internal stress caused by a desolvation shrinkage evenwhen a solvent is used.

[2-2] Hydrolysis and Polycondensation Process

In the present invention, the above-mentioned compound (1), compound (2)and/or oligomers thereof are first subjected to hydrolysis andpolycondensation reaction (hydrolysis and polycondensation process).This hydrolysis and polycondensation reaction can be performed by aknown method. Hereinafter, the compound (1), compound (2) and oligomersthereof are referred to as “material compound” as appropriate, when nodistinction is made among them.

A theoretical amount of water, used for performing the hydrolysis andpolycondensation reaction of the material compound, is based on areaction formula shown by the following formula (3), and it turns out tobe half the molar ratio of the total amount of the hydrolyzable groupsin the system.

[Chemical Formula 5]

2×≡Si—X+H₂O→≡Si—O—Si≡+2×XH  (3)

The above formula (3) represents a case in which M in general formulas(1) and (2) is silicon as an example. “≡Si” and “Si≡” represent three ofthe four bonds held by a silicon atom in an abbreviated manner.

In the present description, the theoretical amount of water required forthe hydrolysis, that is, the amount of water corresponding to half themolar ratio of the total amount of the hydrolizable groups is selectedas a reference (the ratio of hydrolysis is 100%). And therefore, theamount of water used for the hydrolysis is represented as a percentageto this reference value, that is, it is represented as “ratio ofhydrolysis.”

In the present invention, the amount of water used for performing thehydrolysis and polycondensation reaction is, when expressed by theabove-mentioned ratio of hydrolysis, preferably in the range of usually80% or more and particularly 100% or more. If the ratio of hydrolysis islower than this range, the hydrolysis/polymerization (sic) may beinsufficient, and consequently, the material may volatilize during thecuring or the strength of the cured product may be insufficient. If theratio of hydrolysis exceeds 200%, on the other hand, liberated wateralways remains in the system in the course of the curing. This fact maycause the semiconductor element or phosphor to degrade or the cup partto absorb water, which may lead to a cause of the foamings, cracks orpeelings during the curing. What is important in a hydrolysis reactionis to perform the hydrolysis and polycondensation using water of theratio of hydrolysis that is close to 100% or more (for example, 80% ormore). However, by adding a process in which liberated water is removedbefore the coating process, the ratio of hydrolysis even exceeding 200%can be applied. However, in this case, using too much water willincrease the amounts of water to be removed and solvent to be used ascompatibilizer, which may complicate the concentration process or lowerthe coating properties of the member due to an excessivepolycondensation. Thus, it is preferable that the upper limit of theratio of hydrolysis is usually set to 500% or lower, among others, 300%or lower, and preferably 200% or lower.

It is preferable that a catalyst coexists during the hydrolysis andpolycondensation of the material compound, in order to promote thehydrolysis and polycondensation. In this case, the examples of thecatalyst used include: organic acids such as acetic acid, propionic acidand butyric acid; inorganic acids such as nitric acid, hydrochloricacid, phosphoric acid and sulfuric acid; and organometallic compoundcatalysts. For a member to be used for a portion that is directly incontact with the semiconductor device, organometallic compound catalyststhat do not have much effect on the insulating property are preferable.In this context, the organometallic compound catalyst indicates not onlya catalyst comprised of a narrowly-defined organometallic compound, inwhich organic groups are directly bound to metal elements, but also acatalyst comprised of broadly-defined organometallic compound includingorganometallic complexes, metal alkoxides, salts of organic acids andmetals and the like.

Among the organometallic compound catalysts, those containing at leastone element selected from zirconium, hafnium, tin, zinc and titanium arepreferable. Of these, organometallic compound catalysts containingzirconium are particularly preferable.

Concrete examples of the organometallic compound catalyst containingzirconium include: zirconium tetraacetylacetonate, zirconiumtributoxyacetylacetonate, zirconium dibutoxydiacetylacetonate, zirconiumtetranormalpropoxide, zirconium tetraisopropoxide, zirconiumtetranormalbutoxide, zirconium acylate and zirconium tributoxystearate.

Concrete examples of the organometallic compound catalyst containinghafnium include: hafnium tetraacetylacetonate, hafniumtributoxyacetylacetonate, hafnium dibutoxydiacetylacetonate, hafniumtetranormalpropoxide, hafnium tetraisopropoxide, hafniumtetranormalbutoxide, hafnium acylate and hafnium tributoxystearate.

Examples of the organometallic compound catalyst containing titaniuminclude: titanium tetraisopropoxide, titanium tetranormalbutoxide,butyltitanate dimmer, tetraoctyltitanate, titanium acetylacetonato,titanium octyleneglycolate and titanium ethylacetoacetate.

Examples of the organometallic compound catalyst containing zincinclude: zinc stearate, zinc octylate, zinc 2-ethylhexanate and zinctriacetylacetonate.

Examples of the organometallic compound catalyst containing tin include:tetrabutyl tin, monobutyl tin trichloride, dibutyl tin dichloride,dibutyl tin oxide, tetraoctyl tin, dioctyl tin dichloride, dioctyl tinoxide, tetramethyl tin, dibutyl tin laurate, dioctyl tin laurate,bis(2-ethylhexanoate)tin, bis(neodecanoate)tin,di-n-butylbis(ethylhexylmalate)tin,di-normalbutylbis(2,4-pentanedionate)tin, di-normalbutylbutoxychlorotin, di-normalbutyldiacetoxy tin, di-normalbutyldilaurylic acid tin anddimethyldineodecanoate tin.

These organometallic compound catalysts can be used either as a singleone or as a mixture of two or more kinds in any combination and in anyratio.

By using the above-mentioned preferable organometallic compoundcatalyst, it is possible to suppress the formation of by-products,low-molecular-weight cyclic siloxane, at the time of hydrolysis andpolycondensation of the material compound, and to prepare with highyield the semiconductor-device-member formation liquid.

Furthermore, by using the organometallic compound catalyst, thesemiconductor device member of the present invention can be equippedwith excellent heat resistance that satisfies the requirement ofcharacteristic (1) described earlier in the above-mentioned [1-1]. Thereason is not clear. However, it is thought that the aboveorganometallic compound catalyst not only accelerates hydrolysis andpolycondensation reaction of the material compound as catalyst but iscapable of attaching to and dissociating from the silanol ends of thehydrolyzate/polycondensate and its cured product temporarily. Thismechanism is considered to be instrumental in adjusting reactivity ofthe silanol-containing polysiloxane, and brings about, under hightemperature conditions, (i) prevention of oxidation of the organicgroups, (ii) prevention of the formation of unnecessary crosslinkingsamong the polymers, (iii) prevention of cleavage of the main chain orthe like. In the following, these actions (i) to (iii) will beexplained.

(i) Prevention of oxidation of organic groups is thought to be achievedas follows. When a heat-induced radical is formed on, for example, amethyl group a transition metal in the organometallic compound catalystis capable of capturing the radical. On the other hand, the transitionmetal itself loses its ionic valency as a result of the radical captureand, through its interaction with oxygen, it prevents oxidation of theorganic groups. It is inferred that deterioration of the semiconductordevice member is thus suppressed.

(ii) Prevention of the formation of unnecessary crosslinkings among thepolymers is thought to be achieved as follows. For example, a methylgroup is oxidized by oxygen molecules to formaldehyde, leading toformation of a hydroxyl group bonded to a silicon atom. When thehydroxyl groups thus formed are subjected to dehydration condensation,crosslinking points generate among the polymers. If these crosslinkingsincrease, a semiconductor device member, which is originallyrubber-like, may become hard and fragile. However, it is inferred thatthe organometallic compound catalysts are combined with silanol groupsand thus can prevent progress of crosslinkings due to pyrolysis.

(iii) Prevention of cleavage of the main chain or the like is thought tobe achieved as follows. The organometallic compound catalysts combinewith silanols, which prevents the cleavage of the main chain of thepolymer caused by intramolecular attack by the silanol and the weightloss at the time of heating caused by formation of cyclic siloxanes.These mechanisms are considered to lead to improvement in heatresistance.

The proportion of the organometallic compound catalyst used is selectedappropriately depending on the kind of catalyst used. It is usually 0.01weight % or more, preferably 0.05 weight % or more, more preferably 0.1weight % or more, and usually 5 weight % or less, preferably 2 weight %or less, more preferably 1 weight % or less, relative to the totalamount of the material subjected to the hydrolysis and polycondensation.When the proportion of the organometallic compound catalyst is toosmall, it is possible that the curing takes too much time, or themechanical strength or durability is not enough because of insufficientcuring. On the other hand, when the proportion of the organometalliccompound catalyst is too large, it is possible that the control ofphysicochemical property of the cured product, namely the semiconductordevice member, becomes difficult because of too rapid curing, thetransparency of the semiconductor device member is impaired because ofprecipitation of the catalyst due to its inability to be dissolved ordispersed, the semiconductor device member becomes colored when used ata high temperature because the amount of organic material incorporatedin the form of the catalyst is large.

These organometallic compound catalysts can be added to the raw materialsystem in one portion at the time of hydrolysis and polycondensation, orthey can be added in several divided portions. It is possible that asolvent is used to dissolve the catalysts at the time of hydrolysis andpolycondensation, or the catalysts may be dissolved directly in thereaction solution. However, when it is used for the formation liquid fora semiconductor light-emitting device, it is desirable that the solventis distilled off completely after the process of hydrolysis andpolycondensation in order to prevent foaming at the time of curing orcoloration caused by heat.

Incidentally, a solid catalyst is low in solubility. When using such acatalyst dissolved insufficiently, a direct temperature rising causesnonuniform reactions locally, leading possibly to white turbidity in thesystem or formation of insoluble matter in a state of transparent gel.In order to prevent those problems, the following operations can beapplied to the catalyst particles, for example. (i) Pulverizing theparticles to several tens or several hundreds of micrometers using amortar for facilitating their dissolution. (ii) Preheating a resincomposition mixed with the catalyst at 30 to 50° C. while stirring todissolve the catalyst before rising the temperature up to the reactiontemperature. Incidentally, when mixing siloxane materials havingdifferent reactivities, it is recommended that the catalyst is firstadded and dissolved in the material having lower reactivity beforemixing the materials having higher reactivities.

If liquid separation occurs in the system during the hydrolysis andpolycondensation reaction and a nonuniformity is generated, a solventmay be used. As the solvent, for example, lower alcohols of C1 to C3,dimethylformamide, dimethylsulfoxide, acetone, tetrahydrofuran,methylcellosolve, ethylcellosolve, methylethylketone, toluene and watercan be arbitrarily used. Of these, solvents that are neither stronglyacidic nor strongly basic are preferable for reasons of not affectingthe hydrolysis and polycondensation adversely. Solvents can be usedeither as a single one or as a mixture of two or more kinds thereof inany combination and in any ratio. The amount of solvent to be used maybe freely selected, but it is preferable to use a minimum amount of itbecause the solvent is often removed in the process of coating thesemiconductor device. It is also preferable to select a solvent whoseboiling point is 100° C. or lower, preferably 80° C. or lower, in orderto facilitate the removal of the solvent. In some cases, the initialnonuniformity resolves during the reaction because a solvent such asalcohol is generated by the hydrolysis reaction even without the needfor adding a solvent from outside.

The hydrolysis and polycondensation reaction of the above materialcompounds is performed at, in the case of under normal pressure, usually15° C. or higher, preferably 20° C. or higher, more preferably 40° C. orhigher, and usually 140° C. or lower, preferably 135° C. or lower, morepreferably 130° C. or lower. A higher temperature may also be allowed bymaintaining the liquid phase under an increased pressure, but it ispreferable that the temperature does not exceed 150° C.

The reaction time of the hydrolysis and polycondensation reactiondepends on the reaction temperature. But the reaction proceeds over aperiod of usually 0.1 hour or longer, preferably 1 hour or longer, morepreferably 3 hours or longer, and usually 100 hours or shorter,preferably 20 hours or shorter, more preferably 15 hours or shorter. Itis preferable that the reaction time is adjusted as appropriate withcarrying out a molecular weight control.

Under the above hydrolysis and polycondensation conditions, if thereaction time is too short or the reaction temperature is too low, thehydrolysis/polymerization (sic) may be insufficient, leading possibly tothe volatilization of the material during the curing or insufficientstrength of the cured product. On the other hand, if the reaction timeis too long or the reaction temperature is too high, the molecularweight of the polymers may become high and the silanol amount in thesystem may decrease, leading possibly to defective adhesion in thecoating process or crack generations due to a non-uniform structure ofthe cured body caused by a premature curing. Taking the above tendenciesinto consideration, it is preferable to select appropriate conditions inaccordance with the desired physical property values.

After the above hydrolysis and polycondensation reaction terminates, theresultant hydrolyzate/polycondensate is stored at or below roomtemperature until the time of use. However, polycondensation slowlyproceeds also in the meantime and thus it is preferable that thehydrolyzate/polycondensate is usually used within 60 days of storage atroom temperature, after the heated hydrolysis and polycondensationreaction described above terminates, especially when it is used as athick-film member, preferably within 30 days, and more preferably within15 days. The above period can be prolonged if necessary by storing thehydrolyzate/polycondensate in a low temperature range in which thehydrolyzate/polycondensate does not freeze. It is preferable that thestorage period is adjusted as appropriate with carrying out a molecularweight control.

The hydrolyzate/polycondensate (polycondensate) of the above-mentionedmaterial compounds can be obtained by the operations described above.This hydrolyzate/polycondensate is preferably liquid. However, if asolid hydrolyzate/polycondensate can be made liquid using a solvent,such a hydrolyzate/polycondensate can also be used. The liquidhydrolyzate/polycondensate thus obtained is thesemiconductor-device-member formation liquid which will be changed intothe semiconductor device member of the present invention by curing inthe process to be described later.

[2-3] Solvent Distillation

When a solvent is used in the above hydrolysis and polycondensationprocess, it is preferable to distill off, usually before the dryingprocess, the solvent from the hydrolyzate/polycondensate (solventdistillation process). Thereby, a semiconductor-device-member formationliquid (a hydrolyzate/polycondensate in a liquid state) withoutcontaining a solvent can be obtained. As described above, it has beendifficult to handle the hydrolyzate/polycondensate when distilling offthe solvent, because it causes curing of the hydrolyzate/polycondensate.However, when a bifunctional component oligomer is used in theproduction method of the present invention, the solvent can be distilledoff because the reactivity of the hydrolyzate/polycondensate isinhibited and thus the hydrolyzate/polycondensate does not cure evenwith the solvent distillation before the drying process. By distillingoff the solvent before the drying process, crack generations, peelingsand breakings of wires, due to the desolvation shrinkage, can beprevented.

Usually, water used for the hydrolysis is also distilled off when thesolvent is distilled off. Also, solvents to be distilled off include asolvent represented by XH or the like, which is generated by thehydrolysis and polycondensation reaction of the material compoundsrepresented by the general formulas (1) and (2). Furthermore, it alsoincludes low-molecular-weight cyclic siloxane, which is a by-product atthe time of the reaction.

Any method of the solvent distillation may be used as long as theadvantageous effects of the present invention are not seriously damaged.However, it should be avoided to carry out the distillation of thesolvent at a temperature equal to or higher than the curing starttemperature of the hydrolyzate/polycondensate.

A concrete range of the temperature condition for distilling off thesolvent is usually 60° C. or higher, preferably 80° C. or higher, andmore preferably 100° C. or higher, and usually 150° C. or lower,preferably 130° C. or lower, and more preferably 120° C. or lower. Ifthe temperature falls below the lower limit of this range, the solventdistillation may be insufficient. If the temperature exceeds the upperlimit of this range, the hydrolyzate/polycondensate may gelate.

A pressure condition for the solvent distillation is usually normalpressure. Further, the pressure is reduced when necessary so that theboiling point of the reaction liquid during the solvent distillationshould not reach the curing start temperature (usually 120° C. orhigher). The lower limit of the pressure is a level at which the maincomponents of the hydrolyzate/polycondensate are not distilled off.

In general, low-boiling point component can be distilled off efficientlyunder conditions of high temperature and high vacuum. When the amount oflow-boiling point component is very small and its complete removal isdifficult due to the shape of the apparatus, the polymerization reactionmay proceed too far in a high temperature operation and the molecularweight of the product may become too large. Further, when a catalyst ofa specific kind is used, it may lose its catalytic activity under acondition of high temperature for a long period, and thus thesemiconductor-device-member formation liquid may become difficult tocure. Therefore, in those instances, it is possible to distill off thelow-boiling point component at a low temperature and under normalpressure, by means of nitrogen gas blowing-in or by steam distillationas appropriate.

In any case of distillation, such as under reduced pressure or withnitrogen gas blowing-in, it is preferable to increase the molecularweight in the former process to an appropriate extent, hydrolysis andpolycondensation reaction, in order not to distill off the maincomponent of the hydrolyzate/polycondensate.

When the low-boiling point component, such as solvent, water,low-molecular-weight cyclic siloxane formed as by-product or dissolvedair, is removed sufficiently by these means from thesemiconductor-device-member formation liquid, the semiconductor devicemember prepared can decrease the foaming during the curing due tovaporization of the low-boiling point component and the peeling from thedevice during use at high temperatures. This is desirable.

However, the solvent distillation is not an essential operation.Particularly when a solvent whose boiling point is equal to or lowerthan the curing temperature of the hydrolyzate/polycondensate is used,the solvent will be volatilized before the curing of thehydrolyzate/polycondensate starts in the drying process of thehydrolyzate/polycondensate, and thus the generation of cracks and thelike due to the desolvation shrinkage can be prevented without speciallyperforming the solvent distillation process. However, since the volumeof the hydrolyzate/polycondensate may change due to the volatilizationof the solvent, it is preferable to perform solvent distillation, fromthe viewpoint of accurate control of the dimension and shape of thesemiconductor device member.

[2-4] Drying

By drying (drying process or curing process) thehydrolyzate/polycondensate obtained by the above hydrolysis andpolycondensation reaction, the semiconductor device member of thepresent invention can be obtained. The hydrolyzate/polycondensate isusually liquid, as described above. By drying it in a mold of thedesired shape, the semiconductor device member of the present inventionin the desired shape can be formed. Also, by drying thehydrolyzate/polycondensate after applying it on the desired region, thesemiconductor device member of the present invention can be formeddirectly on the desired region. Though the solvent does not necessarilyevaporate in the drying process, the drying process, in this context, isassumed to include a phenomenon in which a hydrolyzate/polycondensatehaving fluidity is hardened by losing the fluidity. Therefore, the above“drying” may be interpreted as “curing” when evaporation of the solventis not involved.

In the drying process, the metalloxane bond is formed by furtherpolymerization of the hydrolyzate/polycondensate, and the polymers aredried and cured, so as to obtain the semiconductor device member of thepresent invention.

During the drying process, the hydrolyzate/polycondensate is heated to apredetermined curing temperature for curing. The concrete temperaturerange can be decided arbitrarily as long as thehydrolyzate/polycondensate can be dried. But it is preferably 120° C. orhigher and more preferably 150° C. or higher because the metalloxanebond is usually formed efficiently at 100° C. or higher. However, if thehydrolyzate/polycondensate is heated together with the semiconductordevice, it is preferable to perform the drying process usually at orbelow the heat-resistant temperature of the device components, andpreferably at 200° C. or lower.

The time for which the curing temperature maintained (namely, curingtime) for drying the hydrolyzate/polycondensate is not unconditionallydetermined because it depends on the concentration of a catalyst used,thickness of the member and the like. However, the drying process isperformed for usually 0.1 hour or more, preferably 0.5 hour or more,more preferably 1 hour or more, and usually 10 hours or less, preferably5 hours or less, more preferably 3 hours or less.

The condition of rising temperature in the drying process is notspecially limited. That is, the temperature may be either maintained ata constant level during the drying process or changed continuously orintermittently. Also, the drying process may be performed as a pluralityof steps. Further, the temperature may be changed stepwise in the dryingprocess. By changing the temperature stepwise, an advantage of beingable to prevent foaming caused by a residual solvent or dissolved watervapor can be achieved. Particularly, when an additional curing at ahigher temperature is performed after a curing at a lower temperature,internal stress is not likely to be generated in the obtainedsemiconductor device member, leading to a further advantage ofgenerating less cracks or peelings.

However, when the above hydrolysis and polycondensation reaction isperformed in the presence of a solvent, if no solvent distillationprocess is performed or a solvent remains in thehydrolyzate/polycondensate even after performing the solventdistillation process, it is preferable that the drying process isdivided into a first drying process in which the solvent issubstantially removed at a temperature equal to or below the boilingpoint of the solvent and a second drying process in which thehydrolyzate/polycondensate is dried at a temperature equal to or abovethe boiling point of the solvent. The “solvent” in this context includesa solvent represented by XH or the like, which is generated by the abovehydrolysis and polycondensation reaction of the above-mentioned materialcompound, and the aforementioned low-molecular-weight cyclic siloxane.The “drying” in the present description refers to a process in which theabove-mentioned hydrolyzate/polycondensate of the material compoundloses the solvent and the metalloxane bond is formed by furtherpolymerization and curing.

The first drying process substantially removes the contained solvent ata temperature equal to or below the boiling point of the solvent withoutactively promoting further polymerization of thehydrolyzate/polycondensate of the material compounds. That is, theproduct obtained in this process is the one in the state of viscousliquid or soft film, due to hydrogen bonds, which is formed byconcentrating the hydrolyzate/polycondensate before the drying process,or the hydrolyzate/polycondensate in a liquid state, which is formed byremoving the solvent.

However, usually the first drying process is preferably performed at atemperature below the boiling point of the solvent. If the first dryingprocess is performed at a temperature equal to or above the boilingpoint of the solvent, the resultant film is foamed by vapor of thesolvent, making it difficult to produce a uniform film without defects.This first drying process may be performed as a single step, if theevaporation of the solvent is efficient, for example when the member isformed into a thin film. However, the temperature may be risen in two ormore steps, if the evaporation efficiency is low, for example when themember is molded in a cup. For a shape for which evaporation efficiencyis extremely low, the hydrolyzate/polycondensate may be coated, afterthe drying/concentration is performed in a separate, more efficientcontainer in advance, in a state still with the fluidity, before furtherdrying is performed. If the evaporation efficiency is low, it ispreferable to contrive to dry a whole member uniformly, not by means ofpromoting the concentration only at the surface of the member, such as aforced-air drying with a large air flow.

In the second drying process, the hydrolyzate/polycondensate is heatedat a temperature equal to or above the boiling point of the solvent andmetalloxane bonds are formed, after the solvent of the abovehydrolyzate/polycondensate is substantially removed in the first dryingprocess, thereby preparing a stable cured product. If a large amount ofsolvent remains during this process, large internal stress is generatedbecause of the proceeding crosslinking reaction and the volume reductiondue to the solvent evaporation, and peelings and cracks occur due to theshrinkage. Since the metalloxane bond is usually formed efficiently at100° C. or higher, the second drying process is performed preferably at100° C. or higher and more preferably at 120° C. or higher. However, ifthe hydrolyzate/polycondensate is heated together with the semiconductordevice, it is preferable to perform the drying process usually at orbelow the heat-resistant temperature of the device components, andpreferably at 200° C. or lower. The curing time in the second dryingprocess is not unconditionally determined because it depends on theconcentration of a catalyst used, thickness of the member and the like.However, the second drying process is performed for usually 0.1 hour orlonger, preferably 0.5 hour or longer, more preferably 1 hour or longer,and usually 10 hours or shorter, preferably 5 hours or shorter, morepreferably 3 hours or shorter.

By separating the process of solvent removal (the first drying process)and the curing process (the second drying process) clearly, as describedabove, the semiconductor device member, having physicochemicalproperties of the present invention and superior in light resistance andheat resistance, can be obtained without inducing crack generations orpeelings, even without the solvent distillation process.

However, it is still possible that the curing may proceed in the firstdrying process or the removal of the solvent may proceed in the seconddrying process. However, the curing in the first drying process or thesolvent removal in the second drying process is usually too subtle toaffect the advantageous effects of the present invention.

The condition of rising temperature in each process is not particularlylimited, as long as the above first drying process and second dryingprocess are substantially realized as described above. That is, thetemperature may be either maintained at a constant level during eachdrying process or changed continuously or intermittently. Also, each ofthe drying processes may be performed in two or more steps. Further, thescope of the present invention is assumed to include such a case thatthe first drying process has a period when the temperature temporarilyrises to or above the boiling point of the solvent or the temperatureduring the second drying process falls below the boiling point of thesolvent, as long as the above process of the solvent removal (the firstdrying process) and the curing process (the second drying process) aresubstantially accomplished independently.

Further, when using a solvent whose boiling point is at or below,preferably below, the curing temperature of thehydrolyzate/polycondensate, the solvent coexisting with thehydrolyzate/polycondensate will be distilled off during the dryingprocess at the moment that the temperature reaches the boiling point,even if the hydrolyzate/polycondensate is heated up to its curingtemperature without performing a specific temperature adjustment.Namely, in this case, the process (the first drying process) ofsubstantially removing the solvent at a temperature at or below theboiling point of the solvent is performed, before thehydrolyzate/polycondensate is cured, in the course of heating thehydrolyzate/polycondensate up to its curing temperature in the dryingprocess. Thereby, the hydrolyzate/polycondensate is formed into a liquidhydrolyzate/polycondensate without a solvent contained therein. Then,after that process, the process (the second drying process) in which thehydrolyzate/polycondensate is cured by drying it at a temperature(namely, the curing temperature) equal to or above the boiling point ofthe solvent will be performed. Therefore, when using a solvent whoseboiling point is equal to or below the above-mentioned curingtemperature, the above-mentioned first drying process and second dryingprocess will be performed even without intending to perform themspecially. Consequently, it is preferable to use a solvent whose boilingpoint is equal to or below, preferably below, the curing temperature ofthe hydrolyzate/polycondensate, because the quality of the semiconductordevice member will not be significantly affected even if thehydrolyzate/polycondensate contains a solvent during the drying process.

[2-5] Others

After the above-mentioned drying process, various types ofpost-treatments may be added on the resultant semiconductor devicemember if necessary. Examples of the post-treatment include a surfacetreatment for improving the adhesion to the mold parts, preparation ofantireflection coating, and preparation of a fine uneven surface forimproving the efficiency of extracting light.

[3] Semiconductor-Device-Member Formation Liquid

The semiconductor-device-member formation liquid of the presentinvention is a liquid material that can be obtained in the process ofhydrolysis and polycondensation, as described above. By curing it in thedrying process, a semiconductor device member can be prepared.

When the semiconductor-device-member formation liquid is a curableorganopolysiloxane, branched organopolysiloxane is more preferable thanstraight-chain organopolysiloxane, from the standpoint of the thermalexpansion coefficients of their cured products. This is because, thethermal expansion coefficient of the cured product of a branchedorganopolysiloxane is smaller than that of a straight-chainorganopolysiloxane, of which cured product is in a state of elastomerhaving large thermal expansion coefficient, and therefore, change inoptical characteristics associated with thermal expansion, of a branchedorganopolysiloxane, is small.

There is no limitation on viscosity of the semiconductor-device-memberformation liquid of the present invention. However, it is usually 20mPa·s or larger, preferably 100 mPa·s or larger, and more preferably 200mPa·s or larger, and usually 1500 mPa·s or smaller, preferably 1000mPa·s or smaller, and more preferably 800 mPa·s or smaller, at a liquidtemperature of 25° C. Incidentally, the above-mentioned viscosity can bemeasured with a RV-type viscosimeter (for example, RV-type viscosimeter“RVDV-II⁺Pro”, manufactured by Brookfield Engineering Laboratories,Inc.).

There is no limitation on the weight-average molecular weight and themolecular weight distribution of the semiconductor-device-memberformation liquid of the present invention. However, the weight-averagemolecular weight (Mw) in terms of polystyrene, measured with GPC (gelpermeation chromatography), is usually 500 or larger, preferably 900 orlarger, more preferably 3200 or larger, and usually 400000 or smaller,preferably 70000 or smaller, more preferably 27000 or smaller. When theweight-average molecular weight is too small, there is a tendency toform air bubbles during curing after the formation liquid is filled intothe container of semiconductor device. When it is too large, there is atendency of the semiconductor-device-member formation liquid to increasein its viscosity with the passage of time even at low temperatures or todeteriorate its filling efficiency into the container of thesemiconductor device.

The molecular weight distribution (Mw/Mn, where Mw means weight-averagemolecular weight and Mn means number-average molecular weight) isusually 20 or smaller, preferably 10 or smaller, and more preferably 6or smaller. When the molecular weight distribution is too large, thereis a tendency of the member to increase in its viscosity with thepassage of time even at low temperatures or to deteriorate its fillingefficiency into the container of the semiconductor device. Incidentally,Mn can be measured in the same way as Mw, with GPC in terms ofpolystyrene.

In addition, it is preferable for the semiconductor-device-memberformation liquid of the present invention to contain lesslow-molecular-weight components having molecular weights at or below aspecific size. More specifically, the proportion of the components whosemolecular weights are 800 or smaller, in areal ratio of GPC, in thesemiconductor device member of the present invention is usually 10% orsmaller, preferably 7.5% or smaller, and more preferably 5% or smaller.When the low-molecular-weight components are too much, there is apossibility of forming air bubbles during the curing of thesemiconductor-device-member formation liquid or decreasing the yield byweight (solid portion content) during the curing due to volatilizationof the main component.

Furthermore, it is preferable for the semiconductor-device-memberformation liquid of the present invention to contain less polymercomponents having molecular weights at or above a specific size. Morespecifically, the molecular weight of which fraction range of highmolecular weight is 5% in the GPC analysis value of thesemiconductor-device-member formation liquid of the present invention isusually 1000000 or smaller, preferably 330000 or smaller, and morepreferably 110000 or smaller. When the fraction range of thehigh-molecular weight side is too wide, there are possibilities of thefollowing actions.

a) The semiconductor-device-member formation liquid increases in itsviscosity with the passage of time even when stored at a lowtemperature.b) Dehydration condensation while storage produces water, which makes iteasier for the semiconductor-device-member formation liquid to be peeledfrom the substrate, package or the like after the semiconductor devicemember is formed on the surface of the substrate, package or the like.c) Because of the high viscosity, the semiconductor-device-memberformation liquid becomes difficult in getting rid of air bubbles duringthe curing.

In summary, it is preferable that the molecular weight range of thesemiconductor-device-member formation liquid of the present inventionfalls in the above-mentioned range. Such a molecular weight range can berealized by any one the following methods, for example.

(i) Using up the unreacted materials by performing the polymerizationreaction sufficiently at the time of the synthesis.(ii) Removing the low-boiling point and low-molecular weight residues bydistilling off the low-boiling point components sufficiently after thesynthesis reaction.(iii) Preventing the molecular weight distribution from getting widerthan necessary by controlling the reaction velocity or the conditions atthe time of the synthesis reaction so as to progress the polymerizationreaction uniformly.

For example when preparing a semiconductor device member using apolycondensate formed by hydrolysis and polycondensation of a specificcompound, as described in “[2] Production method of semiconductor devicemember”, it is preferable to progress the hydrolysis and polymerization(sic) reaction at the time of synthesis of thesemiconductor-device-member formation liquid uniformly while keeping anappropriate reaction velocity. The hydrolysis and polymerization (sic)is performed at usually 15° C. or higher, preferably 20° C. or higher,and more preferably 40° C. or higher, and usually 140° C. or lower,preferably 135° C. or lower, and more preferably 130° C. or lower. Thelength of time for the hydrolysis and polymerization (sic) reaction is,though it differs depending on the reaction temperature, usually 0.1hour or longer, preferably 1 hour or longer, more preferably 3 hours orlonger, and usually 100 hours or shorter, preferably 20 hours orshorter, more preferably 15 hours or shorter. When the reaction time isshorter than the above range, there is a possibility that the molecularweight fails to reach the necessary size or that nonuiform progress ofthe reaction causes residues of the low-molecular-weight materials whilepolymer components also exists. Such problems may lead to the formationof a cured product which is poor in quality or in storage stability. Onthe other hand, when the reaction time is longer than the above range,there is a possibility that the polymerization catalyst deactivates orthat the productivity gets worse due to the long synthesis time.

When the reaction is difficult to proceed because of low reactionactivity of the material, an inert gas such as argon gas, helium gas ornitrogen gas may be flowed if necessary. Then the water or alcoholgenerated during the condensation reaction follows it and can beremoved, which accelerates the reaction.

It is preferable that the reaction time is adjusted as appropriate withcarrying out a molecular weight control by means of GPC and viscositymeasurement. Furthermore, the reaction time is preferably adjusted inconsideration of the heating-up period.

When using a solvent, it is preferable that the solvent distillation isperformed if necessary at a normal pressure. At this point, when theboiling point of the solvent or other low-molecular-weight materials tobe removed is equal to the curing start temperature (usually, 120° C. orhigher), it is preferable to carry out the distillation under reducedpressure if necessary. Depending on the purpose of use, such as forminga thin light guide film, a part of the solvent can be remained for thepurpose of viscosity reduction. In such a case, a solvent different fromthe reaction solvent can be added after the distillation of the reactionsolvent.

It is preferable that the upper and the lower limit of the molecularweight distribution of the semiconductor-device-member formation liquidfall within the above-mentioned range. However, it is not alwaysnecessary for the molecular weight distribution to have only one peak,insofar as it is within that range. For example,semiconductor-device-member formation liquids having different molecularweight distributions can be mixed so as to add another function. In sucha case, the molecular weight distribution curve may have even two ormore peaks. This is in the case, for example, where, to the firstsemiconductor-device-member formation liquid having high molecularweight so that it can equip the semiconductor device member withmechanical strength, a small amount of the second low-molecular-weightsemiconductor-device-member formation liquid containing a large amountof adhesive component is added.

It is preferable that the amount of low-boiling component in thesemiconductor-device-member formation liquid of the present invention issmall as is the case with the semiconductor device member of the presentinvention as described in “[1-4-9] low-boiling component”.

In addition, a minute amount of alkoxy group usually remains in thesemiconductor device member of the present invention. A semiconductordevice member and a semiconductor-device-member formation liquidcontaining less of this terminal alkoxy group show small weight losses,measured with TG-DTA, leading to high heat resistances. The amount ofalkoxy group contained in the semiconductor-device-member formationliquid of the present invention is usually 5 weight % or lower,preferably 3 weight % or lower, and more preferably 0.2 weight % orlower.

The semiconductor-device-member formation liquid may contain anothercomponent, depending on its use. For example when the semiconductordevice member of the present invention is used as a constituent of asemiconductor light-emitting device, the semiconductor-device-memberformation liquid may contain a phosphor, inorganic particle or the like.At this point, a material containing a semiconductor-device-memberformation liquid and a phosphor is referred to as a “phosphorcomposition of the present invention” particularly. Explanations will begiven on these points later, together with an explanation on the use ofthem.

The other components may be used either as a single kind thereof or as amixture of two or more kinds in any combination and in any ratio.

[4] Use of Semiconductor Device Member

The semiconductor device member of the present invention is notparticularly limited in its use and can be used for various purposestypified by a member for sealing (namely, a sealant for) a semiconductorelement or the like. Among others, by using phosphor particles and/orinorganic particles in combination, it can be more suitably used forspecific purposes. Such combined uses of phosphor particles andinorganic particles will be described below.

[4-1] Phosphor

The semiconductor device member of the present invention can be used,for example, as a member for wavelength conversion by dispersing aphosphor in the semiconductor device member, which is molded inside acup of a semiconductor light-emitting device or applied as a thin filmon an appropriate transparent support. A single kind of phosphor can beused alone or as a mixture of two or more kinds in any combination andin any ratio.

[4-1-1] Type of Phosphor

There is no special limitation on the composition of the phosphor.Preferable examples include compositions in which a host crystal such asa metal oxide represented by Y₂O₃ or Zn₂SiO₄, phosphate represented byCa₅(PO₄)₃Cl, and sulfide represented by ZnS, SrS or CaS, is added withan activator or coactivator such as a rare earth metal ion like Ce, Pr,Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm or Yb, or metal ion like Ag, Cu, Au,Al, Mn or Sb.

Preferable examples of the host crystal include sulfides such as(Zn,Cd)S, SrGa₂S₄, SrS and ZnS; oxysulfides such as Y₂O₂S; aluminatecompounds such as (Y,Gd)₃Al₅O₁₂, YAlO₃, BaMgAl₁₀O₁₇,(Ba,Sr)(Mg,Mn)Al₁₀O₁₇, (Ba,Sr,Ca)(Mg,Zn,Mn)Al₁₀O₁₇, BaAl₁₂O₁₉,CeMgAl₁₁O₁₉, (Ba,Sr,Mg)OAl₂O₃, BaAl₂Si₂O₈, SrAl₂O₄, Sr₄Al₁₄O₂₅ andY₃Al₅O₁₂; silicate such as Y₂SiO₅ and Zn₂SiO₄; oxides such as SnO₂ andY₂O₃; borates such as GdMgB₅O₁₀ and (Y,Gd)BO₃; halophosphates such asCa₁₀(PO₄)₆(FCl)₂ and (Sr,Ca,Ba,Mg)₁₀(PO₄)₆Cl₂; phosphates such asSr₂P₂O₇ and (La,Ce)PO₄.

No particular limitation is imposed on the element composition of theabove host crystal and activator/coactivator. Partial substitution withthe element of the same group is possible. Any phosphor obtained can beused so long as it absorbs light in the near ultraviolet to visibleregion and emits visible light.

More concretely, those listed below can be used as phosphor. The listshown below serves just as an example and phosphors that can be used inthe present invention are not limited to these examples. In thefollowing examples, phosphors with different partial structure are shownabbreviated as a group for the sake of convenience. For example, 3compounds of “Y₂SiO₅:Ce³⁺”, “Y₂SiO₅:Tb³⁺” and “Y₂SiO₅:Ce³⁺, Tb³⁺” arecombined as “Y₂SiO₅:Ce³⁺, Tb³⁺” and 3 compounds of “La₂O₂S:Eu”,“Y₂O₂S:Eu” and “(La,Y)₂O₂S:Eu” are combined as “(La,Y)₂O₂S:Eu”.Abbreviated part is indicated by comma-separation.

[4-1-1-1] Red Phosphor

An example of the wavelength range of fluorescence emitted by a phosphorwhich emits red fluorescence (hereinafter referred to as “red phosphor”as appropriate) is such that the peak wavelength thereof is usually 570nm or longer, preferably 580 nm or longer, and usually 700 nm orshorter, preferably 680 nm or shorter.

Examples of such a red phosphor include europium-activated alkalineearth silicon nitride phosphors represented by (Mg,Ca,Sr,Ba)₂Si₅N₈:Eu,which are constituted by fractured particles having red fracturedsurfaces and emit light in the red region, and europium-activated rareearth oxychalcogenide phosphors represented by (Y,La,Gd,Lu)₂O₂S:Eu,which are constituted by growing particles having nearly sphericalshapes typical of regular crystal growth and emit light in the redregion.

Also applicable in the present embodiment is an phosphor, which isdescribed in Japanese Patent Laid-Open Publication (Kokai) No.2004-300247, containing oxynitride and/or oxysulfide, as well as atleast one element selected from the group consisting of Ti, Zr, Hf, Nb,Ta, W and Mo, and an oxynitride having an α-sialon structure in whichall or part of Al element is replaced by Ga element. These are phosphorscontaining oxynitride and/or oxysulfide.

Other examples of red phosphors include: Eu-activated oxysulfide such as(La,Y)₂O₂S:Eu; Eu-activated oxide such as Y(V,P)O₄:Eu and Y₂O₃:Eu;Eu,Mn-activated silicate such as (Ba,Sr,Ca,Mg)₂SiO₄:Eu,Mn and(Ba,Mg)₂SiO₄:Eu,Mn; Eu-activated sulfide such as (Ca,Sr)S:Eu;Eu-activated aluminate such as YAlO₃:Eu; Eu-activated silicate such asLiY₉(SiO₄)₆O₂:Eu, Ca₂Y₈(SiO₄)₆O₂:Eu, (Sr,Ba,Ca)₃SiO₅:Eu andSr₂BaSiO₅:Eu; Ce-activated aluminate such as (Y,Gd)₃Al₅O₁₂:Ce and(Tb,Gd)₃Al₅O₁₂:Ce; Eu-activated nitride such as (Ca,Sr,Ba)₂Si₅N₈:Eu,(Mg,Ca,Sr,Ba)SiN₂:Eu and (Mg,Ca,Sr,Ba)AlSiN₃:Eu; Ce-activated nitridesuch as (Mg,Ca,Sr,Ba)AlSiN₃:Ce; Eu,Mn-activated halophosphate such as(Sr,Ca,Ba,Mg)₁₀(PO₄)₆Cl₂:Eu,Mn; Eu, Mn-activated silicate such as(Ba₃Mg)Si₂O₈:Eu,Mn and (Ba,Sr,Ca,Mg)₃(Zn,Mg)Si₂O₈:Eu,Mn; Mn-activatedgermanate such as 3.5MgO.0.5MgF₂.GeO₂:Mn; Eu-activated oxynitride suchas Eu-activated α-sialon; Eu,Bi-activated oxide such as(Gd,Y,Lu,La)₂O₃:Eu,Bi; Eu,Bi-activated oxysulfide such as(Gd,Y,Lu,La)₂O₂S: Eu,Bi; Eu,Bi-activated vanadate such as(Gd,Y,Lu,La)VO₄:Eu,Bi; Eu, Ce-activated sulfide such as SrY₂S₄:Eu, Ce;Ce-activated sulfide such as CaLa₂S₄:Ce; Eu,Mn-activated phosphate suchas (Ba,Sr,Ca)MgP₂O₇:Eu,Mn and (Sr,Ca,Ba,Mg,Zn)₂P₂O₇:Eu,Mn;Eu,Mo-activated tungstate such as (Y,Lu)₂WO₆:Eu,Mo; Eu, Ce-activatednitride such as (Ba,Sr,Ca)_(x)Si_(y)N_(z):Eu, Ce (x,y,z being an integerof 1 or larger); Eu,Mn-activated halophosphate such as(Ca,Sr,Ba,Mg)₁₀(PO₄)₆(F,Cl,Br,OH):Eu,Mn; Ce-activated silicate such as((Y,Lu,Gd,Tb)_(1−x)Sc_(x)Ce_(y))₂(Ca,Mg)_(1−r)(Mg,Zn)_(2+r)Si_(z−q)Ge_(q)O_(12+δ).

Also applicable as the red phosphor are: red organic phosphor consistingof rare earth ion complex containing anions of such as β-diketonate,β-diketone, aromatic carboxylic acid or Broensted acid as ligand,perylene pigment (for example, dibenzo{[f,f′]-4,4′,7,7′-tetraphenyl}diindeno[1,2,3-cd:1′,2′,3′-1m] perylene),anthraquinone pigment, lake pigment, azo pigment, quinacridone pigment,anthracene pigment, isoindoline pigment, isoindolinone pigment,phthalocyanine pigment, triphenylmethane series basic dye, indanthronepigment, indophenol pigment, cyanine pigment and dioxazine pigment.

Also, among red phosphors, those whose peak wavelength is 580 nm orlonger, preferably 590 nm or longer, and 620 nm or shorter, preferably610 nm or shorter can be suitably used as an orange phosphor. Examplesof such orange phosphors include: (Sr,Ba)₃SiO₅:Eu, (Sr,Mg)₃(PO₄)₂: Sn²⁺,SrCaAlSiN₃:Eu, and Eu-activated oxynitride such as Eu-activatedα-sialon.

[4-1-1-2] Green Phosphor

Examples of the wavelength range of fluorescence emitted by a phosphorwhich emits green fluorescence (hereinafter referred to as “greenphosphor” as appropriate) are such that the peak wavelength thereof isusually 490 nm or longer, preferably 500 nm or longer, and usually 570nm or shorter, preferably 550 nm or shorter.

Examples of such a green phosphor include europium-activated alkalineearth silicon oxynitride phosphors represented by(Mg,Ca,Sr,Ba)Si₂O₂N₂:Eu, which are constituted by fractured particleshaving fractured surfaces and emit light in the green region, andeuropium-activated alkaline earth silicate phosphors represented by(Ba,Ca,Sr,Mg)₂SiO₄:Eu, which are constituted by fractured particleshaving fractured surfaces and emit light in the green region.

Other examples of the green phosphors include: Eu-activated aluminatesuch as Sr₄Al₁₄O₂₅:Eu and (Ba,Sr,Ca)Al₂O₄:Eu; Eu-activated silicate suchas (Sr,Ba)Al₂Si₂O₈:Eu, (Ba,Mg)₂SiO₄:Eu, (Ba,Sr,Ca,Mg)₂SiO₄:Eu and(Ba,Sr,Ca)₂(Mg,Zn)Si₂O₇:Eu; Ce,Tb-activated silicate such asY₂SiO₅:Ce,Tb; Eu-activated borophosphate such as Sr₂P₂O₇—Sr₂B₂O₅:Eu;Eu-activated halosilicate such as Sr₂Si₃O₈-2SrCl₂:Eu; Mn-activatedsilicate such as Zn₂SiO₄:Mn; Tb-activated aluminate such asCeMgAl₁₁O₁₉:Tb and Y₃Al₅O₁₂:Tb; Tb-activated silicate such asCa₂Y₈(SiO₄)₆O₂:Tb and La₃Ga₅SiO₁₄:Tb; Eu,Tb,Sm-activated thiogalate suchas (Sr,Ba,Ca)Ga₂S₄:Eu,Tb,Sm; Ce-activated aluminate such asY₃(Al,Ga)₅O₁₂:Ce and (Y,Ga,Tb,La,Sm,Pr,Lu)₃(Al,Ga)₅O₁₂:Ce; Ce-activatedsilicate such as Ca₃Sc₂Si₃O₁₂:Ce and Ca₃(Sc,Mg,Na,Li)₂Si₃O₁₂:Ce;Ce-activated oxide such as CaSc₂O₄:Ce; Eu-activated oxynitride such asSrSi₂O₂N₂:Eu, (Sr,Ba,Ca)Si₂O₂N₂:Eu and Eu-activated β-sialon;Eu,Mn-activated aluminate such as BaMgAl₁₀O₁₇:Eu; Eu-activated aluminatesuch as SrAl₂O₄:Eu; Tb-activated oxysulfide such as (La,Gd,Y)₂O₂S:Tb;Ce,Tb-activated phosphate such as LaPO₄:Ce,Tb; sulfide such asZnS:Cu,Al,ZnS:Cu,Au,Al; Ce,Tb-activated borate such as(Y,Ga,Lu,Sc,La)BO₃:Ce,Tb, Na₂Gd₂B₂O₇:Ce,Tb and(Ba,Sr)₂(Ca,Mg,Zn)B₂O₆:K,Ce,Tb; Eu,Mn-activated halosilicate such asCa₈Mg(SiO₄)₄Cl₂:Eu,Mn; Eu-activated thioaluminate or thiogallate such as(Sr,Ca,Ba)(Al,Ga,In)₂S₄:Eu; Eu,Mn-activated halosilicate such as(Ca,Sr)₈(Mg,Zn)(SiO₄)₄Cl₂:Eu,Mn.

Also applicable as the green phosphor are: fluorescent dyes such aspyridine-phthalimide condensation product, benzoxadinone compound,quinazoline compound, coumarine compound, quinophthalone compound andnalthalimide (sic) compound; and organic phosphors such as terbiumcomplex having hexylsalicylate as its ligand.

[4-1-1-3] Blue Phosphor

An example of the wavelength range of fluorescence emitted by a phosphorwhich emits blue fluorescence (referred to as “blue phosphor” asappropriate) is such that the peak wavelength thereof is usually 420 nmor longer, preferably 440 nm or longer, and usually 480 nm or shorter,preferably 470 nm or shorter.

Examples of such a blue phosphor include europium-activated bariummagnesium aluminate phosphors represented by BaMgAl₁₀O₁₇:Eu, which areconstituted by growing particles having nearly hexagonal shapes typicalof regular crystal growth and emit light in the blue region,europium-activated calcium halphosphate phosphors represented by(Ca,Sr,Ba)₅(PO₄)₃Cl:Eu, which are constituted by growing particleshaving nearly spherical shapes typical of regular crystal growth andemit light in the blue region, europium-activated alkaline earthchloroborate phosphors represented by (Ca,Sr,Ba)₂B₅O₉Cl:Eu, which areconstituted by growing particles having nearly cubic shapes typical ofregular crystal growth and emit light in the blue region, andeuropium-activated alkaline earth aluminate phosphors represented by(Sr,Ca,Ba)Al₂O₄:Eu or (Sr,Ca,Ba)₄Al₁₄O₂₅:Eu, which are constituted byfractured particles having fractured surfaces and emit light in the blueregion.

Other examples of the blue phosphor include: Sn-activated phosphate suchas Sr₂P₂O₇:Sn; Eu-activated aluminate such as Sr₄AL₁₄O₂₅:Eu,BaMgAl₁₀O₁₇:Eu and BaAl₈O₁₃:Eu; Ce-activated thiogallate such asSrGa₂S₄:Ce and CaGa₂S₄:Ce; Eu-activated aluminate such as(Ba,Sr,Ca)MgAl₁₀O₁₇:Eu and BaMgAl₁₀O₁₇:Eu,Tb,Sm; Eu,Mn-activatedaluminate such as (Ba,Sr,Ca)MgAl₁₀O₁₇:Eu,Mn; Eu-activated halophosphatesuch as (Sr,Ca,Ba,Mg)₁₀(PO₄)₆Cl₂:Eu and(Ba,Sr,Ca)₅(PO₄)₃(Cl,F,Br,OH):Eu,Mn,Sb; Eu-activated silicate such asBaAl₂Si₂O₈:Eu, (Sr,Ba)₃MgSi₂O₈:Eu; Eu-activated phosphate such asSr₂P₂O₇:Eu; sulfide such as ZnS:Ag,ZnS:Ag,Al; Ce-activated silicate suchas Y₂SiO₅:Ce; tungstate such as CaWO₄; Eu,Mn-activated borophosphatesuch as (Ba,Sr,Ca)BPO₅:Eu,Mn, (Sr,Ca)₁₀(PO₄)₆.nB₂O₃:Eu and2SrO.0.84P₂O₅.0.16B₂O₃:Eu; Eu-activated halosilicate such asSr₂Si₃O₈.2SrCl₂:Eu.

Also applicable as the blue phosphor are: fluorescent dyes such asnaphthalimide compound, benzoxazole compound, styryl compound, coumarinecompound, pyrazoline compound and triazole compound; and organicphosphors such as thlium complex.

[4-1-1-4] Yellow Phosphor

An example of the wavelength range of fluorescence emitted by a phosphorwhich emits yellow fluorescence (hereinafter referred to as “yellowphosphor” as appropriate) is as follows. It is preferable that it isusually 530 nm or longer, preferably 540 nm or longer, more preferably550 nm or longer, and usually 620 nm or shorter, preferably 600 nm orshorter, more preferably 580 nm or shorter. If the emission peakwavelength of the yellow phosphor is too short, yellow components may benot enough and the semiconductor light-emitting device may be inferiorin color rendering. If it is too long, the brightness of thesemiconductor light-emitting device may be lowered.

Examples of the yellow phosphor include various phosphors of such asoxide, nitride, oxynitride, sulfide and oxysulfide. Particularlypreferable examples include: garnet phosphors represented by RE₃M₅O₁₂:Ce(here, RE indicates at least one element from Y, Tb, Gd, Lu and Sm, Mindicates at least one element from Al, Ga and Sc), M² ₃M³ ₂M⁴ ₃O₁₂:Ce(here, M², M³ and M⁴ are divalent, trivalent and tetravalent metalelement respectively) or the like, having garnet structures;orthosilicate phosphors represented by AE₂M⁵O₄:Eu (here, AE indicates atleast one element from Ba, Sr, Ca, Mg and Zn, M⁵ indicates at least oneelement from Si and Ge) or the like; oxynitride phosphors in which apart of oxygen, which is a constituent element of the above types ofphosphors, is substituted by nitrogen; and Ce-activated nitridephosphors having CaAlSiN₃ structures such as AEAlSiN₃:Ce (here, AEindicates at least one element from Ba, Sr, Ca, Mg and Zn).

Also applicable as the yellow phosphor are Eu-activated sulfidephosphors such as CaGa₂S₄:Eu, (Ca,Sr)Ga₂S₄:Eu and (Ca,Sr)(Ga,Al)₂S₄:Eu;and Eu-activated oxynitride phosphors having SiAlON structures such asCax(Si,Al)₁₂(O,N)₁₆:Eu.

[4-1-1-5] Other Phosphors

The semiconductor device member of the present invention may containphosphors other than those cited above. For example, the semiconductordevice member of the present invention may be a fluorescent glass inwhich an ionic-state phosphor material or an organic/inorganic phosphorcomponent is dissolved or dispersed uniformly and transparently.

[4-1-2] Particle Diameter of Phosphor

No particular limitation is imposed on the particle diameter ofphosphors used in the present invention. However, the median particlediameter (D₅₀) thereof is usually 0.1 μm or larger, preferably 2 μm orlarger, more preferably 5 μm or larger, and usually 100 μm or smaller,preferably 50 μm or smaller, more preferably 20 μm or smaller. When themedian particle diameter (D₅₀) of the phosphors is within the aboverange, the light emitted from the semiconductor luminous element can bescattered sufficiently, in the semiconductor light-emitting device to bedescribed later. In addition, in such a case, the light emitted from thesemiconductor luminous element is absorbed in the phosphor particlessufficiently, and therefore, not only the wavelength conversion can beperformed highly efficiently but also the light emitted from thephosphors can be radiated in all directions. With this structure, awhite light can be obtained by mixing primary lights from the severalkinds of phosphors, as well as a synthesized light emitted from thesemiconductor light-emitting device can be obtained, having uniformwhiteness and illumination intensity. When the median particle diameter(D₅₀) of the phosphors is larger than the above range, the phosphors cannot fill the space of illuminant portion sufficiently, and therefore,the light emitted from the semiconductor element may not be absorbed inthe phosphors sufficiently, in the semiconductor light-emitting deviceto be described later. When the median particle diameter (D₅₀) of thephosphors is smaller than the above range, emission efficiency of thephosphors will be reduced, and therefore, illumination intensity of thesemiconductor light-emitting device may be reduced.

It is preferable that the particle size distribution (QD) of thephosphor particles is smaller for the purpose of equalizing thedispersion state of the particles in the semiconductor device member.However, the smaller the particle size distribution, the lower theclassification efficiency will be and therefore the higher the cost willbe. For that reason, it is usually 0.03 or larger, preferably 0.05 orlarger, more preferably 0.07 or larger, and usually 0.4 or smaller,preferably 0.3 or smaller, more preferably 0.2 or smaller.

In the present invention, the median particle diameter (D₅₀) andparticle size distribution (QD) can be obtained from a mass-standardparticle size distribution curve. The mass-standard particle sizedistribution curve can be obtained from the measurement of particle sizedistribution by laser diffraction/scattering method, as describedconcretely in the following.

[Method of Measuring Mass-Standard Particle Size Distribution Curve]

(1) Phosphor particles are dispersed in such a solvent as ethyleneglycol under the condition of 25° C. temperature and 70% humidity.(2) Particle size distribution is measured by laser diffraction particlesize analyzer (LA-300, manufactured by HORIBA, Ltd) at particle diameterrange of 0.1 μm to 600 μm.(3) The particle diameter whose integrated value is 50% in thismass-standard particle size distribution curve is represented by “medianparticle diameter D₅₀”. The particle diameters of 25% and 75% integratedvalues are represented by D₂₅ and D₇₅ respectively. QD is defined as(D₇₅−D₂₅)/(D₇₅+D₂₅). Small value of QD means a narrow particle sizedistribution.

Also, the shape of the phosphor particles is not particularly limited aslong as formation of the semiconductor device members is not affected.For example, it is not limited as long as the fluidity or the like ofthe phosphor part formation liquid (namely, liquid for forming thesemiconductor device member containing phosphor, which has the samemeaning as phosphor component) is not affected.

[4-1-3] Surface Treatment of Phosphor

A surface treatment may be performed to the phosphor used in the presentinvention, for the purpose of enhancing the water resistance orpreventing unnecessary aggregation of the phosphor in the semiconductordevice member. Examples of such a surface treatment include a surfacetreatment using organic, inorganic, glass and the like materials asdefined in Japanese Patent Laid-Open Publication (Kokai) No.2002-223008, a coating treatment with metal phosphate as defined inJapanese Patent Laid-Open Publication (Kokai) No. 2000-96045 or thelike, a coating treatment with metal oxide, and known various surfacetreatments such as silica coating.

For example, when metal phosphate is coated on the surface of phosphors,the following steps (i) to (iii) of surface treatment is performedconcretely.

(i) Predetermined amounts of water-soluble phosphate such as potassiumphosphate and sodium phosphate and water-soluble metallic salt of atleast one metal element selected from alkaline earth metals, Zn and Mn,such as calcium chloride, strontium sulfate, manganese chloride and zincnitrate, are mixed in the phosphor suspension liquid and stirred.(ii) Phosphate of at least one metal element, selected from alkalineearth metals, Zn and Mn, is formed in the suspension, and simultaneouslythe metal phosphate formed is deposited on the surface of the phosphors.(iii) Water is removed.

Other preferable examples of surface treatment include, for example, assilica coating, a method in which SiO₂ is deposited by neutralizing aliquid glass, and a method of surface treatment with hydrolyzedalkoxysilane (for example, Japanese Patent Laid-Open Publication (Kokai)No. Hei 3-231987). Of these, the method of surface treatment withhydrolyzed alkoxysilane is preferable from the standpoint of enhancingthe dispersibility.

[4-1-4] Mixing Method of Phosphor

In the present invention, the method of adding phosphor particles is notparticularly limited. If phosphor particles are in a good dispersionstate, it is sufficient only to post-mix phosphor particles into theabove liquid for forming the semiconductor device member. That is, it issufficient to prepare a phosphor part formation liquid, by mixing theliquid for forming the semiconductor device member and the phosphor, andto form the semiconductor device member by using this phosphor partformation liquid. If phosphor particles tend to aggregate, it ispreferable to perform hydrolysis and polycondensation in the presence ofphosphor particles, mixed in advance into the reaction solution(hereinafter referred to as a “solution before hydrolysis” whenappropriate) containing material compounds not yet subjected tohydrolysis. With this procedure, silane coupling processing is conductedin a part of the particles' surfaces and the dispersion state of thephosphor particles is improved.

Some types of phosphor are hydrolyzable. However, in the semiconductordevice member of the present invention, moisture content existspotentially as silanol products and almost no liberated moisture contentexists in a liquid state (semiconductor-device-member formation liquid)before the coating process, and therefore such phosphors can also beused without being hydrolyzed. Also an advantage of easily using suchphosphors together can be obtained, by using thesemiconductor-device-member formation liquid, already hydrolyzed andpolycondensated, after performing dehydration and dealcoholizationprocesses.

Further, when phosphor particles or inorganic particles (to be describedlater) are dispersed in the semiconductor device member of the presentinvention, it is possible to modify the surface of the particles withorganic ligands in order to improve dispersibility. Addition typesilicone resin, which has previously been used as semiconductor devicemember, was liable to undergo curing impairment by these organic ligandsand could not be mixed/cured with particles which had beensurface-treated. This is because platinum series curing catalyst used inaddition reaction type silicone resin interacts strongly with organicligands and loses capability of hydrosilylation, resulting in poorcuring. Examples of these damaging substances include organic compoundscontaining N, P and S, ionic compounds of heavy metals such as Sn, Pb,Hg, Bi and As, and organic compounds containing multiple bond such asacetylene group (flux, amines, vinyl chloride, sulfur vulcanized rubberetc.). On the other hand, the semiconductor device member of the presentinvention is related to condensing-type curing mechanism, which is lessliable to undergo inhibition by these damaging substances. Therefore,the semiconductor device member of the present invention can be usedmore freely in combination with phosphor particles or inorganicparticles, whose surfaces have been improved with organic ligands, or,further, with phosphor components such as complex phosphors. This meansan excellent property as transparent material that is capable ofintroducing binders for phosphors or nano particles with high refractiveindexes.

[4-1-5] Content of Phosphor

The content of the phosphor in the semiconductor device member of thepresent invention can be selected arbitrary insofar as the advantage ofthe present invention is not significantly impaired. Actually, it can beselected freely depending on its form of applications. As regards asemiconductor device emitting white light, which is used for white LED,white-light lighting system or the like, if the entire recess of thepackage including the semiconductor luminous element is filled by meansof potting, with the phosphor dispersed uniformly, the total content ofthe phosphor is usually 0.1 weight % or more, preferably 1 weight % ormore, more preferably 5 weight % or more, and usually 35 weight % orless, preferably 30 weight % or less, more preferably 28 weight % orless.

In the same application form, but when a material with phosphordispersed in a high concentration is coated as a thin film, at theportion apart from the emission surface (for example, the openingsurface of the package with which recess, containing the semiconductorelement, is filled with transparent sealant, or the light-exitingsurface of an external optical element such as glass lid for anair-tight sealing of LED, lens and optical guide plate) of thesemiconductor element of the semiconductor light-emitting device, thetotal content is usually 5 weight % or more, preferably 7 weight % ormore, more preferably 10 weight % or more, and usually 90 weight % orless, preferably 80 weight % or less, more preferably 70 weight % orless.

When a white light is intended to be obtained by mixing the luminescentcolors of the semiconductor element and phosphor, generally a part ofthe light emitted from the semiconductor element passes through thephosphor part. Therefore, in such a case, the concentration of thephosphor tends to be as low as close to the lower limit of theabove-mentioned range. On the other hand, when a white light is obtainedby converting all of the light emitted from the semiconductor elementinto the light with luminescent color of the phosphor, it is preferablethat the concentration of the phosphor is high. Therefore, in such acase, the concentration of the phosphor tends to be as high as close tothe upper limit of the above-mentioned range. If the content of thephosphor is above this range, coating properties may be lowered, or lowefficiency of phosphor utilization, due to an optical interference, maycause reduced brightness of the semiconductor light-emitting device. Ifthe content of the phosphor is below this range, the wavelengthconversion by the phosphor will be insufficient and therefore theintended luminescent color may not be obtained.

An example of the content of phosphor, which is used in thesemiconductor light-emitting device emitting white light, is shownabove. However, the concrete content of the phosphor is not limited tothat and varies widely depending on the intended color, emissionefficiency of the phosphor, color mixing method, specific gravity of thephosphor, film thickness of coating, shape of the device or the like.

The semiconductor-device-member formation liquid of the presentinvention has such advantages as low viscosity, high miscibility withphosphors or inorganic particles and good coating properties that can bemaintained even when high concentration of phosphors or inorganicparticles are dispersed therein, in comparison with the conventionalliquid for forming the semiconductor light-emitting device member suchas epoxy resin and silicone resin. Moreover, it can be of high viscosityas needed by such a method of adjusting the degree of polymerization andadding thixotropic agent like aerosil. Namely, it is very flexible inadjustment of viscosity according to the intended content of phosphors.Therefore, it can provide a coating liquid that can correspond veryflexibly to not only the kinds or shapes of coating objects but also thevarious coating methods such as potting, spin coating and printing.

The content of the phosphor in the semiconductor device member can bedetermined by the following procedure, if the composition of thephosphor can be identified. A phosphor-containing sample is prebakedafter being pulverized so as to remove carbon components, followed byremoving silicon components as hydrofluorosilicic acid by hydrofluoricacid treatment. By dissolving the residue in diluted sulfuric acid, themetal elements, which are the main components, are made into watersolution and the quantity thereof is determined by such known elementalanalyses as ICP, flame analysis and fluorescent X-ray analysis. Then thecontent of the phosphor can be determined by a calculation. If theshapes and particle diameters of the phosphors are uniform and thespecific gravity thereof is known, the content of phosphor can bedetermined, by a simplified method, from the number of the particles perunit area, obtained by image analysis of the cross section of thecoating.

The phosphor content in the phosphor part formation liquid can be set sothat the phosphor content in the semiconductor device member fallswithin the above range. Namely, when the weight of the phosphor partformation liquid is not changed in the drying process, the phosphorcontent in the phosphor part formation liquid will be equal to thephosphor content in the semiconductor device member. On the other hand,when the weight of the phosphor part formation liquid is changed in thedrying process, for example because the phosphor part formation liquidcontains a solvent or the like, the phosphor content in the phosphorpart formation liquid other than the solvent or the like can beconsidered the same as the phosphor content in the semiconductor devicemember.

[4-2] Combined Use of Inorganic Particles (Fillers)

The semiconductor device member of the present invention may, forexample when it is used for a semiconductor light-emitting device,further contain inorganic particles for the purpose of improving theoptical characteristics and workability, or obtaining any of effects <1>to <5> shown below.

<1> By mixing inorganic particles as a light scattering substance intothe semiconductor device member to cause light from the semiconductorlight-emitting device to scatter, the amount of light from thesemiconductor luminous element incident on the phosphor is increased.This improves the efficiency of wavelength conversion and also widensthe angle of spreading light from the semiconductor light-emittingdevice to the outside.

<2> By blending the semiconductor device member with inorganic particlesas a binder, crack generations are prevented.

<3> By blending the semiconductor-device-member formation liquid withinorganic particles as a viscosity modifier, viscosity of the liquid isimproved.

<4> By blending the semiconductor device member with inorganicparticles, the shrinkage thereof is reduced.

<5> By blending the semiconductor device member with inorganicparticles, the refractive index thereof is adjusted so as to improve theefficiency of extracting light.

In this case, it is only necessary to mix an appropriate amount ofinorganic particles into the semiconductor-device-member formationliquid, similarly to the phosphor particles, according to purposes.Effects that can be obtained in this case depend on the type and theamount of inorganic particles to be mixed.

When, for example, an ultrafine particle silica (manufactured by NipponAerosil Co., Ltd., commercial name: AEROSIL#200) with particle diameterof some 10 nm is used as the inorganic particle, the effect of the above<3> is noticeable because thixotropy of the semiconductor-device-memberformation liquid increases.

When a fractured silica or spherical silica whose particle diameter isabout several μm is used as the inorganic oxide particle, it functionsmainly as the aggregate for the semiconductor device member and increasein thixotropy is just a little. Therefore, in such a case, the effectsof the above <2> and <4> are noticeable.

Also, if inorganic particles of about 1 μm in diameter, whose refractiveindex is different from that of the semiconductor device member, areused, the effect of the above <1> is noticeable because the lightscattering at the interface between the semiconductor light-emittingdevice member and the inorganic particles increases.

If inorganic particles, whose refractive index is larger than that ofthe semiconductor light-emitting device member and diameter is 3 to 5nm, more specifically, is equal to or less than the luminous wavelength,are used, the refractive index of the semiconductor device member can beimproved while maintaining transparency thereof. Therefore, in such acase, the effect of the above <5> is noticeable.

Therefore, the type of inorganic particles to be mixed may be selectedaccording to the purposes. Only one type of the inorganic particles maybe selected or a plurality of types of inorganic particles may becombined. Also, in order to improve the dispersibility thereof, asurface treatment may be applied on the particles with a surfacetreatment agent such as a silane coupling agent.

[4-2-1] Type of Inorganic Particles

Exemplified types of inorganic particles to be used include: inorganicoxide particles such as silica, barium titanate, titanium oxide,zirconium oxide, niobium oxide, aluminum oxide, cerium oxide and yttriumoxide; and diamond particles. However, other materials can be alsoselected depending on the purposes and thus the above examples are notlimited.

Inorganic particles may be in any form, depending on the purposes, suchas powder and slurry. However, if the transparency must be maintained,it is preferable to equalize the refractive indexes of the inorganicparticles and the semiconductor device member of the present inventionor to add the particles as transparent sol, which is aqueous or ofsolvent, to the semiconductor-device-member formation liquid.

[4-2-2] Median Particle Diameter of Inorganic Particles

There is no special limitation on the median particle diameter of theseinorganic particles (primary particles). Usually, it is about 1/10 orless that of phosphor particles. More concretely, the following medianparticle diameter is adopted depending on the use. For example when theinorganic particle is used as light scattering agent, the medianparticle diameter thereof falls within preferably 0.1 μm to 10 μm. Forexample when the inorganic particle is used as aggregate, the medianparticle diameter thereof falls within preferably 1 nm to 10 μm. Forexample when the inorganic particle is used as thickener (thixotropicagent), the median particle diameter thereof falls within preferably 10nm to 100 nm. For example when the inorganic particle is used asrefractive index adjusting agent, the median particle diameter thereoffalls within preferably 1 nm to 10 nm.

[4-2-3] Mixing Method of Inorganic Particle

There is no special limitation on the method of mixing inorganicparticles in the present invention. Usually, it is recommended thatmixing is performed with a planetary mixer, similarly to phosphor, whiledefoaming is done. When small particles which are liable to aggregatelike aerosil are mixed, aggregated particles are crushed after mixing,as needed, using a beads mill or three axis roll mill, and then largeparticles which are easy to mix, such as phosphor, can be mixed.

[4-2-4] Content of Inorganic Particle

The content of the inorganic particle in the semiconductor device memberof the present invention can be selected arbitrary insofar as theadvantage of the present invention is not significantly impaired.Actually, it can be selected freely depending on its form ofapplications. For example when the inorganic particle is used as lightscattering agent, the content thereof falls within preferably 0.01 to 10weight %. As another example, when the inorganic particle is used asaggregate, the content thereof falls within preferably 1 to 50 weight %.As still another example, when the inorganic particle is used asthickener (thixotropic agent), the content thereof falls withinpreferably 0.1 to 20 weight %. As still another example, when theinorganic particle is used as refractive index adjusting agent, thecontent thereof falls within preferably 10 to 80 weight %. When theamount of inorganic particle is too small, the desired advantageouseffects may be unobtainable. When the amount is too large, variouscharacteristics such as adhesion to the cured product, transparency andhardness may be affected adversely.

The semiconductor-device-member formation liquid of the presentinvention has such advantages as low viscosity, high misciblility withphosphors or inorganic particles and good coating properties that can bemaintained even when high concentration of phosphors or inorganicparticles are dispersed therein, in comparison with the conventionalliquid for forming the semiconductor light-emitting device member suchas epoxy resin and silicone resin. Moreover, it can be of high viscosityas needed by such a method of adjusting the degree of polymerization andadding thixotropic agent like aerosil. Namely, it is very flexible inadjustment of viscosity according to the intended content of inorganicparticles. Therefore, it can provide a coating liquid that cancorrespond very flexibly to not only the kinds or shapes of coatingobjects but also the various coating methods such as potting, spincoating and printing.

The content of the inorganic particles in the semiconductor devicemember can be measured by the same method as that of the above-describedcontent of phosphor.

The inorganic particle content in the semiconductor-device-memberformation liquid member can be set so that the inorganic particlecontent in the semiconductor device member falls within the above range.Namely, when the weight of the semiconductor-device-member formationliquid is not changed in the drying process, the inorganic particlecontent in the semiconductor-device-member formation liquid will beequal to the inorganic particle content in the semiconductor devicemember. On the other hand, when the weight of thesemiconductor-device-member formation liquid is changed in the dryingprocess, for example because the semiconductor-device-member formationliquid contains a solvent or the like, the inorganic particle content inthe semiconductor-device-member formation liquid other than the solventor the like can be considered the same as the inorganic particle contentin the semiconductor device member.

[4-3] Combined Use of Conductive Filler

Conductive filler may be also contained, for example when thesemiconductor device member of the present invention is used for asemiconductor light-emitting device, for the purpose of addingconductivity and forming an electric circuit at a lower temperature thanthe soldering temperature by means of printing, potting or the like.

Examples of conductive filler to be used include precious metal powdersuch as silver powder, gold powder, platinum powder and palladiumpowder, base metal powder such as copper powder, nickel powder, aluminumpowder, brass powder and stainless steel powder, precious or base metalpowder plated and alloyed with precious metal such as silver, organicresin powder or silica powder coated with precious metal or base metal,and carbon series filler such as carbon black or graphite. However,other materials can also be selected depending on the purposes and thusthe above examples are not limited. Conductive filler may be used eitheras a single kind of them or as a mixture of two or more kinds in anycombination and in any ratio

Conductive filler may be supplied in any form such as powder or slurry,depending on the purpose. When transparency needs to be maintained orprint formation with fine wiring is necessary, it is preferably added tothe semiconductor-device-member formation liquid as transparent solwhich is aqueous or of solvent with no aggregation or as nano particlepowder with its surface modified to allow easy redispersion.

Examples of the form of these metal powders includes flake (scale),sphere, grain, dendrite, and three-dimensional aggregation of primaryparticles of sphere. Of these, the use of silver powder as maincomponent is preferable from the standpoint of conductivity, cost andreliability. In terms of conductivity, combined use of silver powder anda small amount of carbon black and/or graphite is more preferable.Further, from the standpoint of conductivity and reliability, the use ofsilver powder in the form of flake or sphere is preferable, and thecombined use of flake and sphere silver powder is most preferable.Further, inorganic filler such as silica, talc, mica, barium sulfate orindium oxide can be added in a small amount, if considered appropriate.

Preferable proportion (weight ratio) of silver powder and carbon blackand/or graphite micropowder is as follows. On the supposition that thetotal amount of silver powder and carbon black and/or graphitemicropowder is 100 weight ratio, the upper limit of silver powder ispreferably 99.5 weight ratio or less, more preferably 99 weight ratio orless, and the lower limit is 85 weight ratio or more, preferably 90weight ratio or more.

There is no special limitation on the median particle diameter of theconductive filler. Usually, it is 0.1 μm or larger, preferably 0.5 μm orlarger, more preferably 1 μm or larger, and usually 50 μm or smaller,preferably 20 μm or smaller, more preferably 10 μm or smaller.Particularly when transparency or micro manipulation is required, it isusually 3 nm or larger, preferably 10 nm or larger, and usually 150 nmor smaller, preferably 100 nm or smaller.

The content of conductive filler is usually 50 weight % or more,preferably 75 weight % or more, and more preferably 80 weight % or more,assuming that the combined amount of the conductive filler and thebinder resin is 100 weight %. From the standpoint of adhesiveness andink viscosity, it is usually 95 weight % or less, preferably 93 weight %or less, and more preferably 90 weight % or less. When the amount ofconductive filler is too small, the desired advantageous effects may beunobtainable. When the amount is too large, various characteristics suchas adhesion to the cured product, transparency and hardness may beaffected adversely.

The semiconductor-device-member formation liquid of the presentinvention has such advantages as low viscosity, high miscibility withphosphors or inorganic particles and good coating properties that can bemaintained even when high concentration of phosphors or inorganicparticles are dispersed therein, in comparison with the conventionalliquid for forming the semiconductor light-emitting device member suchas epoxy resin and silicone resin. Moreover, it can be of high viscosityas needed by such a method of adjusting the degree of polymerization andadding thixotropic agent like aerosil. Namely, it is very flexible inadjustment of viscosity according to the intended content of inorganicparticles. Therefore, it can provide a coating liquid that cancorrespond very flexibly to not only the kinds or shapes of coatingobjects but also the various coating methods such as potting, spincoating and printing.

The content of the inorganic particles in the semiconductorlight-emitting device member can be measured by the same method as thatof the above-described content of phosphor.

[4-4] Combined Use with Other Members

The semiconductor device member of the present invention may be used asa sealant singly. However, it may also be used together with anothermember for more complete cutoff of oxygen or moisture for example whenit seals an organic phosphor, a phosphor that is liable to deteriorateby oxygen or moisture, a semiconductor light-emitting device or thelike. In such a case, an air-tight sealing, using such a highlyair-tight sealant as glass plate or epoxy resin, or vacuum sealing maybe added from outside of the member of the present invention, which isprovided for retention of the phosphor, sealing the semiconductorelement or extracting light. In this case, the shape of the device isnot specially limited. Namely, it is enough for the sealant, coating orcoated layer, made of the semiconductor device member of the presentinvention, to be substantially protected and blocked from outside by anair-tight material such as metal, glass or highly air-tight resin, so asto allow no passage of oxygen and moisture.

In addition, the semiconductor device member of the present inventionmay be used as adhesive agent for a semiconductor device because itexcels in adhesion as described above. More specifically, for example,the semiconductor device member of the present invention can be used forbonding a semiconductor element and a package, a semiconductor elementand a sub mount, package constituents together, a semiconductor deviceand an external optical element, by means of application, printing orpotting. Since the semiconductor device member of the present inventionexcels particularly in light resistance and heat resistance, it providesa semiconductor light-emitting device with high reliability enough tostand a long-time use, when it is used as adhesive agent for ahigh-power semiconductor light-emitting device that is exposed to hightemperature or ultraviolet rays for a long time.

The semiconductor device member of the present invention can achievesufficient adhesion just by itself. However, for more sufficientadhesion, various surface treatments for improving adhesion may beperformed on the surface that will be directly in contact with thesemiconductor device member. Examples of such surface treatment include:a formation of an adhesion-improving layer using a primer or a silanecoupling agent, a chemical surface treatment using such an agent asacids or bases, a physical surface treatment using plasma irradiation,ion irradiation or electron beam irradiation, a surface-rougheningprocedure by sandblasting, etching or microparticles coating. Otherexamples of the surface treatment for improving adhesion include knownsurface treatment methods such as described in Japanese Patent Laid-OpenPublication (Kokai) No. Hei 5-25300, “Hyomen Kagaku”, Vol. 18 No. 9, pp21-26, written by Norihiro Inagaki, and “Hyomen Kagaku”, Vol. 19 No. 2,pp 44-51 (1998), written by Kazuo Kurosaki.

[5] Semiconductor Light-Emitting Device [5-1] (A) Package

The package used in the semiconductor light-emitting device of thepresent invention is characterized in that the surface material thereofcontains one or more of Si, Al and Ag. In this context, the “package”means a member in the semiconductor light-emitting device, on which the(B) semiconductor element, to be described later, is mounted. Shapes ofthe package include: a cup shape, a flat plate with a recess formedtherein, a flat plate with a weir formed therearound, and a flat plate.A cup-shaped one is usually used.

[5-1-1] Surface Material

The surface material of the package used in the semiconductorlight-emitting device of the present invention is characterized in thatit contains one or more of Si, Al and Ag.

The package is a member on which the (B) semiconductor element ismounted, as described above. Various surface treatments are providedthereon for the purpose of improving brightness (reflectance),durability/heat resistance, light resistance, adhesion, heat dissipatingproperty and the like. Particularly in a power device, it is oftensubjected to a surface treatment and the material thereof is oftenselected for the purpose of improving durability and heat resistance.

The concrete examples include: a surface treatment such as silverplating for improving the reflectance, and thus the brightness, or thelike; a selection of a ceramic package based on SiN_(x), SiC, SiO₂, Al,AlN, Al₂O₃ or the like for improving heat dissipating property,insulation property, heat resistance, durability, light resistance andthe like; and a treatment of the ceramic surface such as surfacesmoothing or roughening by means of forming an inorganic coating layerfor improving the reflectance or adding the light diffusivity.

Even when utilizing a package with such specific surface treatments, thesemiconductor light-emitting device of the present invention exhibitsexcellent characteristics without such a problem of peeling of itssealant.

The content of Si and Al contained in the surface material of thepackage used in the semiconductor light-emitting device of the presentinvention is, in the surface material, usually 5 weight % or more,preferably 10 weight % or more, and more preferably 40 weight % or more,and usually 100 weight % or less, preferably 90 weight % or less, andmore preferably 80 weight % or less. The above-mentioned contentindicates the total content of Si and Al, in a surface where SiO₂ andAl₂O₃ are solid-solved and mixed, such as a surface of an Al₂O₃ ceramicsintered compact using SiO₂ as sintering agent. On the other hand, in asurface of a material comprising two layers, such as a reinforcedplastic containing an inorganic filler like a glass fiber, it indicatesthe Si content in the reinforced plastic. Ag exists frequently at a highpurity as a plated metal in the semiconductor light-emitting device. TheAg content in an Ag-containing surface is usually 60 weight % or more,preferably 70 weight % or more, more preferably 80 weight % or more, andusually 100 weight % or less, preferably 98 weight % or less, morepreferably 95 weight % or less. When the above-mentioned content is toosmall, there is a possibility of failing in achieving variousadvantageous effects of the surface treatment or the like. When it istoo large, it is possible that the manipulation is obstructed or theceramic composition deviates from the intended one.

[5-1-2] Other Materials

The aforementioned surface material constitutes the whole of or a partof the material of the package used in the semiconductor light-emittingdevice of the present invention. The other material than the surfacematerial contained partially in the package can be selected arbitrarilyaccording the purpose. It can be usually selected to be used fromorganic materials, inorganic materials, glass materials and combinationsof them, as appropriate.

The organic materials include: organic resins such as polycarbonateresin, polyphenylene sulfide resin, epoxy resin, acrylic resin, siliconeresin, ABS (acrylonitrile-butadiene-styrene) resin, nylon resin,polyphthalamide resin and polyethylene resin; and reinforced plasticssuch as those in which such organic resins and a glass filler or aninorganic powder are mixed for improvement in heat resistance ormechanical strength and decrease in thermal expansion coefficient.

The inorganic materials include: ceramics materials such as SiN_(x),SiC, SiO₂, AlN and Al₂O₃; metal materials such as iron, copper, brass,aluminium, nickel, gold, silver, platinum and palladium; and theiralloys.

The glass materials include: low-melting glasses used for a hermeticseal part or an adhesion between members; and optical glasses used as apart of the package such as a window or a transparent lid of thepackage.

When the semiconductor light-emitting device of the present invention isused in a so-called power device, which is high in amount of heatgeneration and luminescence, materials having higher durabilities thansemiconductor light-emitting devices of the conventional constitutionscan be selected. In such a power device, inorganic materials, which aresuperior in durabilities such as heat resistance and light resistance,are more preferable than organic materials, which are prone todeterioration such as discoloration. In particular, materials superiorin workability and heat dissipating property, such as copper, aluminium,SiN_(x), AlN, Al₂O₃, are preferable. In addition, various surfacetreatments such as silver plating may be provided onto these packagematerials for the purpose of improving the reflectance, and thus thebrightness, as described before.

[5-1-3] Shape

There is no special limitation on the shape of the package used for thesemiconductor light-emitting device of the present invention. Packagesfor known semiconductor light-emitting devices or packages forsemiconductor light-emitting devices, which are improved as appropriateaccording to various purposes, can be used. Concrete examples of theshape include: a ceramic package in which the reflector is integratedwith the substrate; one in which a heat sink made of copper, aluminiumor the like is provided immediately below the luminous element; and oneof which reflector has a reflection plane coated with silver. Shapes ofthe package include: a cup shape, a flat plate with a recess formedtherein, a flat plate with a weir formed therearound, and a flat plate.A cup-shaped one is usually used.

As package used for the semiconductor light-emitting device of thepresent invention, ones commercially available can be used. The concreteexamples include: a model number of “3PINMETAL” (whose reflectormaterial is a silver-plated copper and hermetic seal around the pin ismade of a low-melting glass) manufactured by MCO Co., ltd.; and a modelnumber of “M5050N” (whose reflector material and substrate material isAl₂O₃, electrode material is Ag—Pt, and adhesion portion between thereflector and the substrate is made of a low-melting glass) manufacturedby Kyoritsu Elex Co., Ltd.

[5-2] (B) Semiconductor Element [5-2-1] Semiconductor Element

As semiconductor element used in the semiconductor light-emitting deviceof the present invention, a light-emitting diode (LED), semiconductorlaser diode (LD) or the like can be used concretely.

The concrete examples thereof include: GaN-based compound semiconductor,ZnSe-based compound semiconductor and ZnO-based compound semiconductor.Among them, a GaN-based LED or LD, which utilizes a GaN-based compoundsemiconductor, is preferable. This is because a GaN-based LED andGaN-based LD have light output and external quantum efficiency fargreater than those of an SiC-based LED and the like that emit the samerange of light, and therefore, they can give very bright luminescencewith very low electric power when used in combination with the phosphorto be described later (sic). For example, a GaN-based LED and GaN-basedLD have usually 100 or more times higher emission intensity thanSiC-based ones, with respect to the same current load. Among GaN-basedLEDs and LDs, ones having Al_(x)Ga_(y)N luminous layers, GaN luminouslayers or In_(x)Ga_(y)N luminous layers are preferable. Among GaN LEDsin particular, the one having In_(x)Ga_(y)N luminous layer isparticularly preferable because emission intensity thereof is then veryhigh. Among GaN LDs, the one having a multiple quantum well structure ofIn_(x)Ga_(Y)N layer and GaN layer is particularly preferable becauseemission intensity thereof is then very high.

In the above description, the X+Y usually takes a value in the range of0.8 to 1.2. A GaN-based LED having the above-mentioned kind of luminouslayer that is doped with Zn or Si or without any dopant is preferablefor the purpose of adjusting the luminescent characteristics.

A GaN-based LED contains, as its basic components, a such kind ofluminous layer, a p layer, an n layer, an electrode and a substrate.Among them, a GaN-based LED having such a heterostructure as sandwichingthe luminous layer with n type and p type of Al_(x)Ga_(y)N layers, GaNlayers, In_(x)Gay_(N) layers or the likes is preferable, from thestandpoint of high emission efficiency. Moreover, the one whoseheterostructure is replaced by a quantum well structure is morepreferable because it can have higher emission efficiency.

Methods of crystal layer growth by which a GaN-based semiconductorelement is formed include: HVPE method, MOVPE method and MBE method.HVPE method is preferable when preparing a thick film. MOVPE method orMBE method is preferable when preparing a thin film.

In the semiconductor light-emitting device of the present invention, itis particularly preferable to use a surface-emitting type luminous body,particularly surface-emitting type GaN-based laser diode, as the lightemitting device, because the emission efficiency of the whole lightemitting device can be enhanced then. A surface-emitting type luminousbody means a luminous body having high luminescence in the direction ofthe film surface. In a surface-emitting type GaN-based laser diode, theluminescence not in the direction of the edge of the luminous layer butin the direction of the surface thereof can be intensified, by means ofcontrolling the crystal growth of the luminous layer or the like and, atthe same time, adjusting the reflective layer or the like sufficiently.Using a surface-emitting type makes it possible for the emission crosssection per unit amount of light to be larger, in comparison with a typein which light emits from the edge of the luminous layer.

[5-2-2] Emission-Peak Wavelength

The emission-peak wavelength of the semiconductor element used in thesemiconductor light-emitting device of the present invention can haveany wavelength in the range between visible to near-ultraviolet. Theemission-peak wavelength of the semiconductor element is an importantfactor. It relates to the excitation efficiency of the phosphor and thusthe conversion efficiency from the phosphor-exciting light to thephosphor, and also influences the durability of the sealant. In thesemiconductor light-emitting device of the present invention, a luminouselement having a luminous wavelength in usually near-ultraviolet regionto blue region is used. More specifically, a luminous element of whichpeak luminous wavelength is usually 300 nm or longer, preferably 330 nmor longer, more preferably 350 nm or longer, and usually 900 nm orshorter, preferably 500 nm or shorter, more preferably 480 nm or shorteris used. When it is too short, the sealant absorbs the luminouswavelength, leading to the failure in realizing a device with highbrightness, and a thermal degradation of the device arises due to theheat generation, which are unfavorable.

[5-2-3] Size of Emission Surface

The semiconductor light-emitting device of the present invention isespecially excellent in the use of a high-power device, namely powerdevice. Therefore, when it is used in a power device, the area of theemission surface of the (B) semiconductor element (chip) is usually 0.15mm² or larger, preferably 0.2 mm² or larger, more preferably 0.3 mm² orlarger, and usually 10 mm² or smaller, preferably 5 mm² or smaller, morepreferably 3 mm² or smaller. When the area of the emission surface istoo small, it is difficult to be used for a power device.

In this context, the emission surface means the p-n composition surface.When multiple small-sized chips are mounted on one package, theabove-mentioned area means the total area of them.

Incidentally, the shape of the chip itself is usually rectangular orsquare, in view of loss reduction in the wafer cutting.

Accordingly, when the chip is rectangular and the emission surfacecomprises that of only one chip, the long side of the emission surfaceis usually 0.43 mm or longer, preferably 0.5 mm or longer, morepreferably 0.6 mm or longer, and usually 4 mm or shorter, preferably 3mm or shorter, more preferably 2 mm or shorter. And, the short sidethereof is usually 0.35 mm or longer, preferably 0.4 mm or longer, morepreferably 0.5 mm or longer, and usually 2.5 mm or shorter, preferably 2mm or shorter, more preferably 1.5 mm or shorter.

When the chip is square, each side of the emission surface is usually0.38 mm or longer, preferably 0.45 mm or longer, more preferably 0.55 mmor longer, and usually 3.1 mm or shorter, preferably 2.2 mm or shorter,more preferably 1.7 mm or shorter.

[5-2-4] Surface Temperature of Emission Surface

The semiconductor light-emitting device of the present invention isespecially excellent in the use of a high-power device, namely powerdevice. Therefore, when it is used in a power device, the surfacetemperature of the emission surface of the (B) semiconductor element(chip) during operation is usually 80° C. or higher, preferably 85° C.or higher, more preferably 90° C. or higher, and usually 200° C. orlower, preferably 180° C. or lower, more preferably 150° C. or lower.When the surface temperature of the emission surface is too low, it isdifficult to be used for a power device. Exceedingly high surfacetemperature of the emission surface may make it difficult to dissipatethe heat or pass the current uniformly. When the surface temperature ofthe emission surface gets too high, it is preferable that thedeterioration of the semiconductor and its peripheral members isinhibited by providing a heat sink or a radiation fin in the vicinity ofthe device.

[5-2-5] Surface Material

The surface material of the semiconductor element used in thesemiconductor light-emitting device of the present invention ischaracterized in that it contains one or more of Si, Al and Ag.

SiN_(x) and SiO₂ are usually unnecessary as a protective layer for thesemiconductor element (chip). Chips without these protective layers canbe used. However, for GaN, which is a “hard” material in physicochemicalterms and needs a large energy for its manipulation, it is preferable toprovide a protective layer from the standpoint of proper manipulation.Namely, SiN, layer, SiC layer and SiO₂ layer are protective layers thatprevent effects from plasma, chemical agents and oxidizing environmentsin the process of manipulation. They also serve as protections fromstatic electricity, migration of impure metals and solder sticking, andas light extracting films. However, in any cases, the protective layeris provided in a process before the GaN is cut into individual chips,and therefore, it is inevitable for the product chip to have a lateralside without a protective layer. In other words, the protective layerusually exists in a form covering a part of the chip.

The expression of “chip” in the present invention contains theprotective layer. The entire surface may be covered with the protectivelayer. However, a surface from which an electrode is taken out andlateral sides actually have no protective layers thereon. The thicknessof the above-mentioned protective layer is usually sufficiently small incomparison with the thickness of the GaN layer of the chip body orsubstrate, for the purpose of securing the accuracy of themicrofabrication. Namely, the thickness of the above-mentionedprotective layer is usually 1000 nm or smaller, preferably 500 nm orsmaller, and usually 1 nm or larger, preferably 10 nm or larger. Whenthe film thickness is too small, there is a possibility of insufficientprotection effect. When it is too large, there is a possibility ofhindering the microfabrication.

Al and Ag are rarely used as a protective layer on an LED chip, becausethey are opaque. However, Al is used for an (insulating) substrate to beformed with GaN luminous layer of the chip, in the form of sapphire(Al₂O₃).

The content of Si, Al and Ag contained in the surface material of thesemiconductor element used in the semiconductor light-emitting device ofthe present invention is usually 40 weight % or more, preferably 50weight % or more, and more preferably 60 weight % or more, and usually100 weight % or less, preferably 90 weight % or less, and morepreferably 80 weight % or less. In this context, when a thin protectivelayer formed of SiNx, SiO₂ or the like and of which thickness is severalhundreds of nanometers exists on the surface of the emission surface ofthe semiconductor element, the material of this protective layer istaken as the surface composition. When the above-mentioned content istoo small, various advantageous effects of the surface treatment or thelike will not be exhibited sufficiently. When it is too large, theopaque layer formed will affect the light output adversely or theceramic composition will deviate from the intended one.

[5-2-6] Surface State and Shape of Chip

The surface state of the chip may be either smooth or rough. However, itis preferable that it does not cause unnecessary diffused reflection inorder not to affect the efficiency of extracting light adversely. Whenit is smooth, it is preferable that the entire shape of the chip isfabricated so that the total reflexion of the light emitted from theemission surface can be prevented. When it is rough, the one formed witha microstructure suitable for extracting light with a pitch preferablyequal to the luminous wavelength or shorter, and more preferably equalto a quarter of the luminous wavelength or shorter, is preferablebecause it can realize a high efficiency of extracting light. Aroughened surface, though it is difficult to be fabricated so that awide protective layer containing Si is provided (remained), has anadvantageous effect of improved adhesivity due to the enlarged contactarea when the wide protective layer is provided. In addition, in asemiconductor element having an SiC substrate or sapphire substrate,when a flip-chip mounting is formed on the substrate of which surface isroughened, it is preferable that the surface containing Si and Al is incontact with the sealant to be described later as widely as possible,because the adhesion between them is higher then. In both cases of theabove-mentioned smooth surface and roughened surface, it is necessaryfor the semiconductor light-emitting device of the present invention tohave a surface layer containing Si, so as to improve the adhesiveness tothe sealant of the present invention. And, it is preferable that theratio of the surface area of the layer containing Si, relative to thetotal surface area of the chip (exclusive of adherends by means ofsolder or silver paste), is 5% or larger and 90% or smaller. The shapeof the chip itself is usually rectangular or square, in view of lossreduction in the wafer cutting.

[5-2-7] Chip Substrate

The material of the substrate can be selected as appropriate, from SiC,SiO₂, sapphire, GaN and AlN, for example, depending on the purpose.Among them, SiC, SiO₂ and sapphire, which contains Al, are preferablebecause they show high adhesion to the sealant used in the semiconductorlight-emitting device of the present invention. When using a substratewithout containing Si or Al, it is preferable that a coating layercontaining Si (SiN_(x), SiO₂) is provided on the side of the emissionsurface of the chip.

[5-3] (C) Sealant

The (C) sealant used in the semiconductor light-emitting device of thepresent invention (hereinafter referred to as “the sealant of thepresent invention” arbitrarily) is characterized in that it satisfiesall of the following conditions (i) to (iii). Also, it possiblysatisfies another requirement to be described later, if necessary.

(i) The sealant has a functional group capable of forming a hydrogenbond with oxygen in a metalloxane bond or a hydroxyl group, which ispresent on the surface of a ceramic or a metal.

(ii) The maintenance rate of transmittance with respect to light of400-nm wavelength before and after kept at temperature of 200° C. for500 hours is 80% or more and 110% or less.

(iii) The maintenance rate of transmittance with respect to the light of400-nm wavelength before and after being irradiated with light havingwavelength of 370 nm or longer and center wavelength of 380 nm andradiant intensity of 0.6 kW/m² for 72 hours is 80% or more and 110% orless.

In the following, the requirements (i) to (iii) and another requirementwill be described in detail.

[5-3-1] (i) Functional Group

The sealant of the present invention comprises a functional groupcapable of forming a hydrogen bond with a predetermined functional group(for example, a hydroxyl group or oxygen in a metalloxane bond) that ispresent on the surface of a ceramic or a metal. As described above, thesurface of a (A) package or a (B) semiconductor element is usuallyformed of or coated with ceramic or metal. Also, a hydroxyl groupusually exists on the surface of a ceramic and a metal. On the otherhand, the sealant of the present invention usually comprises afunctional group capable of forming a hydrogen bond with that hydroxylgroup. Therefore, the sealant of the present invention is superior inadhesion to the (A) package or (B) semiconductor element, due to theabove-mentioned hydrogen bond.

Functional groups of the sealant of the present invention that can bebound to the hydroxyl group through hydrogen bond include, for example,silanol and alkoxy group. At this point, only one functional group ortwo or more types thereof may be used.

Whether the sealant of the present invention has any functional groupthat can be bound to the hydroxyl group through hydrogen bond, asdescribed above, can be checked by a technique of spectroscopy such assolid Si-NMR, solid ¹H-NMR, infrared absorption spectrum (IR) and Ramanspectrum.

[5-3-2] (ii) Heat Resistance

The sealant of the present invention is superior in heat resistance.That is, it has a property that transmittance thereof with respect tothe light having a predetermined wavelength hardly varies even when leftunder a high temperature condition. More specifically, the maintenancerate of transmittance of the sealant of the present invention withrespect to the light having a wavelength of 400 nm before and afterbeing kept for 500 hours at temperature of 200° C. is usually 80% ormore, preferably 90% or more, and more preferably 95% or more, andusually 110% or less, preferably 105% or less, and more preferably 100%or less.

The above ratio of variation can be measured in the same way as themethod of measuring the transmittance, described earlier in [1-4-3], bymeans of measuring transmittance using an ultraviolet/visiblespectrophotometer.

[5-3-3] (iii) UV Resistance

The sealant of the present invention is superior in light resistance.That is, it has a property that transmittance thereof with respect tothe light having a predetermined wavelength hardly varies even whenirradiated with UV (ultraviolet light). More specifically, themaintenance rate of transmittance with respect to the light of 400-nmwavelength of the sealant of the present invention before and afterbeing irradiated with light having wavelength of 370 nm or longer andcenter wavelength of 380 nm and radiant intensity of 0.6 kW/m² for 72hours is usually 80% or more, preferably 90% or more, and morepreferably 95% or more, and usually 110% or less, preferably 105% orless, and more preferably 100% or less.

The above ratio of variation can be measured in the same way as themethod of measuring the transmittance, described earlier in [1-4-3], bymeans of measuring transmittance using an ultraviolet/visiblespectrophotometer.

[5-3-4] Other Physicochemical Properties

The sealant of the present invention is mainly characterized by theabove-mentioned characteristics. For such a sealant, inorganic materialsand/or organic materials can be used.

Examples of the inorganic materials include metal alkoxide, ceramicprecursor polymer, a solution obtained by hydrolytic polymerization of asolution containing metal alkoxide by sol-gel method, and inorganicmaterials obtained by solidifying combinations of such materials (forexample, inorganic materials containing siloxane bond).

Examples of the organic materials include thermoplastic resin,thermosetting resin and light curing resin. More specifically, theexamples include: methacrylic resin such as polymethacrylate methyl;styrene resin such as polystyrene, styrene-acrylonitrile copolymer;polycarbonate resin; polyester resin; phenoxy resin; butyral resin;polyvinyl alcohol; cellulose resin such as ethyl cellulose, celluloseacetate and cellulose acetate butyrate; epoxy resin; phenol resin; andsilicone resin. Of these, a silicon-containing compound can bepreferably used from the standpoint of high heat resistance, high lightresistance and the like, particularly when a high-power light emittingdevice such as a lighting system is required, even though epoxy resinhas been generally used as phosphor-dispersing material for asemiconductor light-emitting device conventionally.

Silicon-containing compound means a compound of which molecular containsa silicon atom. Examples thereof include organic materials (siliconematerials) such as polyorganosiloxane, inorganic materials such assilicon oxide, silicon nitride and silicon oxynitride, and glassmaterials such as borosilicate, phosphosilicate and alkali silicate.Among them, silicone materials are preferable because the handling iseasy or the cured product has stress relaxation characteristics.Silicone resins for semiconductor light-emitting devices were disclosedas follows, for example. In Japanese Patent Laid-Open Publication(Kokai) No. Hei 10-228249, Japanese Patent Publication No. 2927279, andJapanese Patent Laid-Open Publication (Kokai) No. 2001-36147, it is usedas a sealant. In Japanese Patent Laid-Open Publication No. 2000-123981,it is used as a wavelength-adjustment coating.

[5-3-4A] Silicone Material

Silicone material usually indicates organic polymers having a siloxanebond as the main chain. Examples thereof include compounds representedby the general composition formula and/or mixtures of them.(R¹R²R³SiO_(1/2))_(M)(R⁴R⁵SiO_(2/2))_(D)(R⁶SiO_(3/2))_(T)(SiO_(4/2))_(Q)

In the above formula, R¹ to R⁶ can be the same as or different from eachother, and are selected from the group consisting of organic functionalgroup, hydroxyl group and hydrogen atom. M, D, T and Q are a number of 0or greater and smaller than 1 respectively, and they satisfiesM+D+T+Q=1.

When a silicone material is used for sealing a semiconductor luminouselement, a liquid silicone material can be used by being solidified withheat or light after it seals the element.

When categorizing silicone materials based on the curing mechanism, theyusually fall into such categories as addition polymerization-curabletype, polycondensation-curable type, ultraviolet ray-curable type andperoxide vulcanized type. Of these, preferable are additionpolymerization-curable type (addition type silicone resin) andcondensation-curable type (condensing type silicone resin) andultraviolet ray-curable type. In the following, addition type siliconematerial and condensing type silicone material will be explained.

[5-3-4A-1] Addition Type Silicone Material

Addition type silicone material represents a material in whichpolyorganosiloxane chain is cross-linked by means of organic additionalbond. Typical example includes a compound having an Si—C—C—Si bond asthe crosslinking point, which can be obtained through a reaction betweenvinylsilane and hydrosilane in the presence of an addition type catalystsuch as Pt catalyst. As such compounds, commercially available ones canbe used. For example, as concrete commercial names of an additionpolymerization-curable type can be cited “LPS-1400”, “LPS-2410” and“LPS-3400”, manufactured by Shin-Etsu Chemical Co., Ltd.

For example, the above-mentioned addition type silicone material can beobtained concretely by mixing an (A) alkenyl group-containingorganopolysiloxane represented by the following average compositionformula (1a) and a (B) hydrosilyl group-containing organopolysiloxanerepresented by the following average composition formula (2a) andreacting them in the presence of a (C) addition-reaction catalyst in acatalyst quantity. At that time, the quantitative ratio of the mixed (A)and (B) is such that the total amount of the hydrosilyl group of (B) is0.5 to 2.0 times more than the total amount of the alkenyl group of (A).

The (A) alkenyl group-containing organopolysiloxane is anorganopolysiloxane in which each one molecular thereof, represented bythe following composition formula (1a), contains at least two alkenylgroups bound to respectively a silicon atom.

R_(n)SiO_([(4−n)/2])  (1a)

(In the formula (1a), R represents an univalent hydrocarbon group,alkoxy group or hydroxyl group which has identical or differentsubstituents or does not have substituents, n is a positive numbersatisfying 1≦n<2, where, at least one of R is an alkenyl group.)

The (B) hydrosilyl group-containing polyorganosiloxane is an organohydrogen polysiloxane in which each one molecular thereof, representedby the following composition formula (2a), contains at least twohydrogen atoms bound to respectively a silicon atom.

R′_(a)H_(b)SiO_([(4−a−b)/2])  (2a)

(In the formula (2a), R′ represents an univalent hydrocarbon groupexclusive of alkenyl group, which has identical or differentsubstituents or does not have substituents, a and b are positive numberssatisfying 0.7≦a≦2.1, 0.001≦b≦1.0 and 0.8≦a+b≦2.6.)

In the following, more detailed explanation will be given on theaddition type silicone resin.

Regarding the R, of the above-mentioned formula (1a), being an alkenylgroup, it is preferably an alkenyl group of which carbon number is 2 to8, such as vinyl group, allyl group, butenyl group and pentenyl group.Further, when the R is a hydrocarbon group, it is preferably selectedfrom univalent hydrocarbon groups of which carbon numbers are 1 to 20,such as alkyl groups like methyl group and ethyl group, vinyl group, andphenyl group. More preferably, it is methyl group, ethyl group or phenylgroup. The Rs may be different from each other. However, when UVresistance is required, it is preferable for 80% or more of the Rs to bemethyl groups. The R may be alkoxy group or hydroxyl group of whichcarbon number is 1 to 8. However, the content of alkoxy group andhydroxyl group is preferably 3% or less in the weight of the (A) alkenylgroup-containing organopolysiloxane.

In the above-mentioned composition formula (1a), n is a positive numbersatisfying 1≦n<2. When it is 2 or larger, sufficient mechanical strengthfor a sealant can not be achieved. When it is smaller than 1, it isdifficult to synthesize this organopolysiloxane.

The (A) alkenyl group-containing organopolysiloxane may be used as asingle kind thereof or two or more kinds in any combination and in anyratio.

Next, the (B) hydrosilyl group-containing polyorganosiloxane functionsas a cross-linking agent for curing the composition through ahydrosilylation reaction with the (A) alkenyl group-containingorganopolysiloxane.

In the composition formula (2a), R′ represents an univalent hydrocarbongroup exclusive of alkenyl group. As R′, the same groups as those for Rin the composition formula (1a) (exclusive of alkenyl group, however)can be cited. When UV resistance is required, it is preferable for atleast 80% or more of the R's to be methyl groups.

In the composition formula (2a), a is a positive number of usually 0.7or larger, preferably 0.8 or larger, and usually 2.1 or smaller,preferably 2 or smaller, and b is a positive number of usually 0.001 orlarger, preferably 0.01 or larger, and usually 1.0 or smaller,preferably 1.0 or smaller, where a+b is 0.8 or larger, preferably 1 orlarger, and 2.6 or smaller, preferably 2.4 or smaller.

In addition, each one molecular of the (B) hydrosilyl group-containingpolyorganosiloxane contains at least two SiH bonds, and preferably threeor more SiH bonds.

The molecular structure of the (B) hydrosilyl group-containingpolyorganosiloxane may be either straight, cyclic, branched or ofthree-dimensional network. Its number of silicon atoms (or degree ofpolymerization) per one molecular should be of the order of 3 to 1000,particularly 3 to 300.

The (B) hydrosilyl group-containing polyorganosiloxane may be used as asingle kind thereof or two or more kinds in any combination and in anyratio.

The proportion of the above-mentioned (B) hydrosilyl group-containingpolyorganosiloxane depends on the total amount of the alkenyl groups ofthe (A) alkenyl group-containing organopolysiloxane. More specifically,the total molar amount of the SiH of the (B) hydrosilyl group-containingpolyorganosiloxane can be usually 0.5 times or more, preferably 0.8times or more, and usually 2.0 times or less, preferably 1.5 times orless than the total molar amount of the alkenyl groups of the (A)alkenyl group-containing organopolysiloxane.

The (C) addition-reaction catalyst is a catalyst to accelerate thehydrosilylation addition reaction of the SiH groups in the (B)hydrosilyl group-containing polyorganosiloxane and the alkenyl groups inthe (A) alkenyl group-containing organopolysiloxane. This (C)addition-reaction catalyst includes, for example: platinum-containingcatalysts such as platinum black, platinum bichloride, chloroplatinicacid, reactants of chloroplatinic acid and univalent alcohol, complexesof chloroplatinic acid and olefins, and platinum bisacetoacetate; andplatinum-group metallic catalysts such as palladium catalyst and rhodiumcatalyst.

The (C) addition-reaction catalyst may be used either as a single kindthereof or as a mixture of two or more kinds in any combination and inany ratio.

The proportion of the addition-reaction catalyst used may be catalystquantity. When it is a metal of platinum group, it is preferable for itto be added at usually 1 ppm or higher, particularly 2 ppm or higher,and 500 ppm or lower, particularly 100 ppm or lower, in the total weightof the (A) alkenyl group-containing organopolysiloxane and (B)hydrosilyl group-containing polyorganosiloxane.

To the composition for forming the addition type silicone material, anaddition-reaction inhibitor for enhancing the hardenability and the potlife may be added as an optional component, in addition to theabove-mentioned (A) alkenyl group-containing organopolysiloxane, (B)hydrosilyl group-containing polyorganosiloxane and (C) addition-reactioncatalyst, insofar as the advantageous effect of the present invention isnot impaired. Also, for adjusting the hardness and the viscosity, astraight-chain diorganopolysiloxane having an alkenyl group, astraight-chain unreactive organopolysiloxane, or a straight-chain orcyclic low-molecular-weight organopolysiloxane of which silicon atomnumber is around 2 to 10 may be added, for example, insofar as theadvantageous effect of the present invention is not impaired.

No particular limitation is imposed on the curing condition of theabove-mentioned composition. However, it is preferable to be at atemperature of 120° C. to 180° C. and for a period of 30 minutes to 180minutes. When the obtained cured product is soft and gelatinous evenafter the curing, the linear expansion coefficient thereof is largerthan that of a silicone resin in a rubber or rigid plastic state. Thegeneration of internal stress can be inhibited then, by means of curingfor 10 to 30 hours at a low temperature close to the room temperature.

As the addition type silicone material, any known ones can be used.Furthermore, it can be introduced with an additive or organic group forimproving the adhesion to metals or ceramics. Silicone materialsdisclosed in Japanese Patent Publications No. 3909826 and No. 3910080and Japanese Patent Laid-Open Publications (Kokai) No. 2003-128922, No.2004-221308 and No. 2004-186168 are preferable, for example.

[5-3-4A-2] Condensing Type Silicone Material

Examples of a condensing type silicone material include a compoundhaving an Si—O—Si bond as the crosslinking point, which can be obtainedthrough hydrolysis and polycondensation of alkyl alkoxysilane.

Concrete examples include polycondensates obtained by performinghydrolysis and polycondensation of the compounds represented by thefollowing general formulas (1b) and/or (2b), and/or oligomers thereof.

M^(m+)X_(n)Y¹ _(m−1)  (1b)

(In the formula (1b), M represents at least one element selected fromsilicon, aluminum, zirconium and titanium, X represents a hydrolyzablegroup, Y¹ represents a univalent organic group, m represents an integerof 1 or larger representing the valence of M, and n represents aninteger of 1 or larger representing the number of X groups, where m≧n)

(M^(s+)X_(t)Y¹ _(s−t−1))_(u)Y²  (2b)

(In the formula (2b), M represents at least one element selected fromsilicon, aluminum, zirconium and titanium, X represents a hydrolyzablegroup, Y¹ represents a univalent organic group, Y² represents a u-valentorganic group, s represents an integer of 1 or larger representing thevalence of M, t represents an integer of 1 or larger and s−1 or smaller,and u represents an integer of 2 or larger.)

As the curing catalyst, a metal chelate compound or the like can be usedpreferably, for example. The metal chelate compound preferably containsat least one of Ti, Ta, Zr, Hf, Zn and Sn. It more preferably containsZr.

As the condensing type silicone material, any known ones can be used.For example, semiconductor light-emitting device members disclosed inJapanese Patent Laid-Open Publications (Kokai) No. 2006-77234, No.2006-291018, No. 2006-316264, No. 2006-336010, No. 2006-348284, and thepamphlet of International Publication No. 2006/090804 are preferablyused.

Among them, it is preferable that the semiconductor device member of thepresent invention is used as the sealant for the semiconductorlight-emitting device of the present invention. This is because thesemiconductor device member of the present invention described aboveusually has, in addition to the characteristics that the (C) sealantshould have, excellent characteristics described earlier.

In the following, explanation will be given with reference toembodiments of the semiconductor light-emitting device. In eachembodiment below, semiconductor light-emitting device is abbreviated as“light-emitting device” when appropriate. The sealant used in thesemiconductor light-emitting device will be referred to as the“semiconductor light-emitting device member”, and it is assumed that, asthe sealant, the semiconductor device member of the present invention isused. In addition, in which part of the semiconductor light-emittingdevice to use the semiconductor light-emitting device member of thepresent invention will be summarized after all the embodiments have beendescribed. However, these embodiments are used only for convenience ofdescription, and therefore, the examples of the light-emitting devices(semiconductor light-emitting devices) of the present invention are notlimited to these embodiments.

[5-4] Basic Concept

Application examples A) and B) of the semiconductor light-emittingdevices using the semiconductor light-emitting device member of thepresent invention are shown below. In both application examples, thesemiconductor light-emitting device member of the present inventionshows superiority in light resistance and heat resistance, less frequentcrack generations and peelings, as well as less degradation inbrightness, compared to conventional semiconductor light-emitting devicemembers. Therefore, a member exhibiting high reliability over a longperiod of time can be provided, by the semiconductor light-emittingdevice member of the present invention.

A) Semiconductor light-emitting devices utilizing the luminescent colorof the luminous element just as it is

B) Semiconductor light-emitting devices that emit light of desiredwavelengths utilizing fluorescence, by means of disposing a phosphorpart near the luminous element so as to make the phosphor or phosphorcomponents in the phosphor part be excited by the light from theluminous element

The semiconductor light-emitting device member of the present inventionof application example A) can be used even singly as a highly durablesealant, light extracting film, and various functional-componentsretaining agents, by utilizing its high durability, transparency, andsealing properties. Particularly when the semiconductor light-emittingdevice member of the present invention is used as functional-componentretaining agent for retaining the above-mentioned inorganic particles orthe like so as to, for example, enhance the refractive index of thesemiconductor light-emitting device member of the present inventionwhile maintaining transparency, the reflection on the light exitingsurface of the luminous element can be reduced, which then leads to theenhancement in efficiency of extracting light, by using thesemiconductor light-emitting device member of the present invention thatis in close contact with the light exiting surface of the luminouselement and making the member have a refractive index approximatelyequal to that of the luminous element.

Also, the semiconductor light-emitting device member of the presentinvention of application example B) can demonstrate superiorcapabilities similar to those in the above-mentioned application exampleA). In addition, it makes possible to form a phosphor part that ishighly durable and can extract light with high efficiency, by retaininga phosphor or phosphor components. Further, when the semiconductorlight-emitting device member of the present invention retains acomponent for enhancing refractive index while maintaining transparencyin addition to the phosphor or phosphor components, the interfacereflection can be reduced, which then leads to the enhancement inefficiency of extracting light, by adjusting the refractive index of thesemiconductor light-emitting device member of the present invention tobe approximately equal to that of the luminous element or the phosphor.

A basic concept of each embodiment to which the semiconductorlight-emitting device member of the present invention is applied will bedescribed below with reference to FIG. 50( a) and FIG. 50( b). FIG. 50(a) and FIG. 50( b) are explanatory drawings of the basic concept of eachembodiment. FIG. 50( a) corresponds to the above application example A)and FIG. 50( b) corresponds to the above application example B).

As shown in FIG. 50( a) and FIG. 50( b), the light emitting device(semiconductor light-emitting device) 1A, 1B of each embodimentcomprises a luminous element 2 comprised of an LED chip and asemiconductor light-emitting device member 3A, 3B of the presentinvention, disposed close to the luminous element 2.

However, in embodiments (Embodiments A-1 and A-2) corresponding to theabove application example A), as shown in FIG. 50( a), light emittingdevice 1A does not contain any phosphor or phosphor component insemiconductor light-emitting device member 3A. In this case,semiconductor light-emitting device member 3A performs various functionssuch as sealing of luminous element 2, extracting light and retainingfunctional components. In the description below, semiconductorlight-emitting device member 3A containing no phosphor or phosphorcomponent will be called a “transparent member” when appropriate.

On the other hand, in embodiments (Embodiments B-1 to B-41)corresponding to the above application example B), as shown in FIG. 50(b), the light emitting device 1B contain a phosphor or phosphorcomponent in semiconductor light-emitting device member 3B. In thiscase, semiconductor light-emitting device member 3B can perform afunction of wavelength conversion, in addition to the functions that canbe performed by semiconductor light-emitting device member 3A in FIG.50( a). In the description below, semiconductor light-emitting devicemember 3B containing a phosphor or phosphor component will be called a“phosphor part” when appropriate. The phosphor part may be shown bynumerals 33 and 34 according to its shape or functions when appropriate.

Luminous element 2 is comprised of an LED chip emitting blue light orultraviolet light, but it may be an LED chip of other luminescent color.

Transparent member 3A performs various functions of such as a highlydurable sealant for luminous element 2, light extracting film andvarious-functions adding film. Transparent member 3A may be used alone.Or otherwise, it can contain any additives, excluding the phosphor andphosphor components, as long as the advantage of the present inventionis not significantly impaired.

Phosphor part 3B, on the other hand, can perform not only functions ofsuch as a highly durable sealant for luminous element 2, lightextracting film and various-functions adding film, but also a functionof wavelength conversion, that is, a function to emit light of thedesired wavelength after the excitation by the light from luminouselement 2. Phosphor part 3B has to contain at least a phosphor materialthat emits light of the desired wavelength after being excited by thelight from luminous element 2. Examples of such a phosphor materialinclude various phosphors exemplified above. Luminescent colors of thelight that can be emitted by phosphor part 3B include white of afluorescent lamp and yellow of a light bulb, as well as three primarycolors red (R), green (G) and blue (B). In summary, phosphor part 3B hasa wavelength conversion function for emitting light of the desiredwavelength that is different from that of the excitation light.

In the above light emitting device 1A shown in FIG. 50( a), light 4emitted from luminous element 2 passes through transparent member 3Abefore being emitted out of light emitting device 1A. Therefore, inlight emitting device 1A, light 4 emitted from luminous element 2 willbe used unchanged in luminescent color of the light emitted fromluminous element 2.

In light emitting device 1B shown in FIG. 50( b), on the other hand,light 4 a, a portion of the light emitted from luminous element 2,passes through phosphor part 3B unchanged before being emitted out oflight emitting device 1B. Also in light emitting device 1B, light 4 b,another portion of the light emitted from luminous element 2, isabsorbed by phosphor part 3B, resulting in that phosphor part 3B isexcited and light 5 having wavelengths specific to phosphor componentscontained in phosphor part 3B, such as phosphor particles, fluorescentions and fluorescent dyes, is emitted out of light emitting device 1B.

Therefore, a synthesized light 6 synthesized from light 4 a, which haspassed through phosphor part 3B after being emitted from luminouselement 2, and light 5, which is emitted from phosphor part 3B, will beradiated from light emitting device 1B as a light with convertedwavelength. The luminescent color of the whole light emitted from lightemitting device 1B will be determined by the luminescent color ofluminous element 2 and that of phosphor part 3B. In this context, light4 a, which passes through phosphor part 3B after being emitted fromluminous element 2, is not always necessary.

[5-5] Embodiments A. Embodiments that do not Use Fluorescence EmbodimentA-1

In light emitting device 1A of the present embodiment, as shown in FIG.1, luminous element 2 is surface-mounted on an insulating substrate 16on which printed wiring 17 is carried out. In luminous element 2, ap-type semiconductor layer (not shown) and an n-type semiconductor layer(not shown) in a luminous layer part 21 are connected electrically toprinted wirings 17 and 17 via conductive wires 15 and 15 respectively.Conductive wires 15 and 15 have a small cross section so that the lightemitted from luminous element 2 may not be blocked.

As luminous element 2, one that emits light of any wavelengths, fromultraviolet to infrared regions, may be used. In this embodiment, agallium nitride LED chip is assumed to be used. In luminous element 2,an n-type semiconductor layer (not shown) is formed on the lower side inFIG. 1 and a p-type semiconductor layer (not shown) is formed on theupper side in the same. The upper side of FIG. 1 is assumed to be thefront side in the following description because light output isextracted from the side of the p-type semiconductor layer.

A frame-shaped frame 18 encircling luminous element 2 is fixed ontoinsulating substrate 16. A sealing part 19 for sealing and protectingluminous element 2 is provided inside frame 18. This sealing part 19 isformed of transparent member 3A, which is the semiconductorlight-emitting device member of the present invention, and the formationthereof can be performed by potting with the above liquid for formingthe semiconductor light-emitting device member.

Thus, because light emitting device 1A of the present embodiment isprovided with luminous element 2 and transparent member 3A, the lightresistance and heat resistance of light emitting device 1A can beimproved. Moreover, since crack generations and peelings are less likelyto occur in sealing part 3A, the transparency in sealing part 3A can beincreased.

Further, the light color unevenness and light color fluctuations can bereduced and also the efficiency of extracting light to the outside canbe enhanced, in comparison with conventional light emitting devices.This is because sealing part 3A can be made to be transparent withoutclouding and turbidity. For that reason, light emitting device 1A issuperior in homogeneity of light color with almost no light colorfluctuations among light emitting devices 1A, and also can enhance theefficiency of extracting light from luminous element 2 to the outsidewhen compared with conventional light emitting devices. Also, theweather resistance of the luminescent material can be enhanced and thusthe lifetime of light emitting device 1A can be prolonged in comparisonwith conventional devices.

Embodiment A-2

Light emitting device 1A of the present embodiment is structured, asshown in FIG. 2, in the same manner as the above embodiment A-1, exceptthat the front side of luminous element 2 is covered with transparentmember 3A and sealing part 19, formed on member 3A. Sealing part 19 isformed of a material different from that of transparent member 3A.Transparent member 3A on the surface of luminous element 2 is atransparent thin film, functioning as a light extracting film andsealing film. Transparent member 3A can be formed, for example, bycoating the above liquid for forming the semiconductor light-emittingdevice member, by a method of spin coating or the like, during theformation process of a chip of luminous element 2. Meanwhile, the samecomponents as in embodiment A-1 are designated by the same referencenumerals to omit redundant explanations.

Thus, because light emitting device 1A of the present embodiment is alsoprovided with luminous element 2 and transparent member 3A, likeembodiment A-1, the light resistance and heat resistance of lightemitting device 1A can be improved. Moreover, since crack generationsand peelings are also less likely to occur in sealing part 3A, thetransparency in sealing part 3A can be increased.

Further, other advantages, like those of embodiment A-1, can be alsoobtained.

B. Embodiments Using Fluorescence Embodiment B-1

Light emitting device 1B of the present embodiment is provided, as shownin FIG. 3( a), with luminous element 2 comprised of an LED chip and amold part 11 obtained by forming a light-transmissible and transparentmaterial into a shell type shape. Mold part 11 covers luminous element2. Luminous element 2 is electrically connected to lead terminals 12 and13, formed of a conductive material. Lead terminals 12 and 13 are formedof a lead frame.

Luminous element 2 is comprised of a gallium nitride LED chip. Inluminous element 2, an n-type semiconductor layer (not shown) is formedon the lower side in FIG. 3( a) and a p-type semiconductor layer (notshown) is formed on the upper side in the same. The upper sides of FIG.3( a) and FIG. 3( b) are assumed to be the front sides in the followingdescription because light output is extracted from the side of thep-type semiconductor layer. The rear surface of luminous element 2 isjoined to a mirror (cup part) 14, which is attached to the front endportion of lead terminal 13 by die bonding. Luminous element 2, in whichthe above p-type semiconductor layer and n-type semiconductor layer areconnected to conductive wires (for example, gold wires) 15 and 15 bybonding respectively, is electrically connected to lead terminals 12 and13 via conductive wires 15 and 15. Conductive wires 15 and 15 have asmall cross section so that the light emitted from luminous element 2may not be blocked.

Mirror 14 has a function to reflect light emitted from both lateralsides and the rear surface of luminous element 2 forward. The lightemitted from the LED chip and that reflected by mirror 14 in the frontdirection are emitted forward via the front end portion of mold part 11,which functions as a lens. Mold part 11 covers luminous element 2 alongwith mirror 14, conductive wires 15 and 15, and a part of lead terminals12 and 13, so that the degradation of various characteristics ofluminous element 2, due to a reaction with moisture in the air or thelike, is prevented. The rear ends of lead terminals 12 and 13 projectfrom the rear surface of mold part 11.

In luminous element 2, as shown in FIG. 3( b), luminous layer part 21,composed of a gallium nitride semiconductor, is formed on phosphor part3B by means of a semiconductor process. A reflecting layer 23 is formedon the rear surface of phosphor part 3B. Light emitted from luminouslayer part 21 is radiated in all directions, but a part of that light,which is absorbed by phosphor part 3B, excites phosphor part 3B andinduces a radiation of light having wavelength specific to theabove-mentioned phosphor components. This light, emitted from phosphorpart 3B, is reflected by reflecting layer 3 (sic) before being emittedforward. Therefore, a synthesized light, synthesized from the lightemitted from luminous layer part 21 and that emitted from phosphor part3B, is obtained by light emitting device 1B.

Thus, light emitting device 1B of the present embodiment is providedwith luminous element 2 and phosphor part 3B, which emits light of thedesired wavelength after being excited by the light from luminouselement 2. Here, if phosphor part 3B is superior in light-transmission,a portion of the light emitted from luminous element 2 is emittedunchanged to the outside, and the phosphor components, which play therole of luminescent center, are excited by another portion of the lightemitted from luminous element 2 and emits light, which is specific tothe phosphor components, to the outside. Thus, it becomes possible toobtain a light, synthesized from the light emitted from luminous element2 and that emitted from phosphor components of phosphor part 3B, andalso to reduce the light color unevenness and light color fluctuations,as well as to enhance the efficiency of extracting light to the outsidein comparison with conventional devices. That is, if phosphor part 3B ishighly transparent without clouding and turbidity, light emitting device1B is superior in homogeneity of light color with almost no light colorfluctuations among light emitting devices 1B, and also can enhance theefficiency of extracting light from luminous element 2 to the outsidewhen compared with conventional light emitting devices. Also, theweather resistance of the luminescent material can be enhanced and thusthe lifetime of light emitting device 1B can be prolonged in comparisonwith conventional devices.

Also in light emitting device 1B of the present embodiment, phosphorpart 3B serves also as a substrate for forming luminous element 2, andtherefore the phosphor components in the phosphor part, which play therole of luminescent center, can efficiently be excited by a part of thelight from luminous element 2, leading to the enhancement in brightnessof the emitted light specific to the phosphor components.

Embodiment B-2

In light emitting device 1B of the present embodiment, as shown in FIG.4, luminous element 2 is surface-mounted on an insulating substrate 16on which printed wiring 17 is carried out. Here, luminous element 2 isstructured in the same manner as in embodiment B-1, in which luminouslayer part 21, composed of a gallium nitride semiconductor, is formed onphosphor part 3B and reflecting layer 23 is formed on the rear surfaceof phosphor part 3B. In luminous element 2, a p-type semiconductor layer(not shown) and an n-type semiconductor layer (not shown) in a luminouslayer part 21 are connected electrically to printed wirings 17 and 17via conductive wires 15 and 15 respectively.

A frame-shaped frame 18 encircling luminous element 2 is fixed ontoinsulating substrate 16. A sealing part 19 for sealing and protectingluminous element 2 is provided inside frame 18.

Thus, since light emitting device 1B in the present embodiment is alsoprovided with luminous element 2 and phosphor part 3B, which emits lightof the desired wavelength after being excited by the light from luminouselement 2, similarly to Embodiment B-1, a light, synthesized from thelight from luminous element 2 and the light from the phosphor, can beobtained. Also, like Embodiment B-1, it becomes possible to reduce thelight color unevenness and light color fluctuations, enhance theefficiency of extracting light to the outside, and as well as prolongthe lifetime, in comparison with conventional devices.

Embodiment B-3

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-2. However, frame18 (see FIG. 4) described in Embodiment B-2 is not used and, as shown inFIG. 5, the shape of sealing part 19 is different. Meanwhile, the samecomponents as in embodiment B-2 are designated by the same referencenumerals to omit redundant explanations.

Sealing part 19 of the present embodiment comprises a sealing functionpart 19 a in a truncated cone shape for sealing luminous element 2 and alens function part 19 b in a lens shape to function as a lens at thefront end portion of sealing part 19.

Thus, light emitting device 1B of the present embodiment can reduce thenumber of components, compared with Embodiment B-2, allowing theminiaturization and weight reduction. Moreover, by providing lensfunction part 19 b functioning as a lens at one portion of sealing part19, distribution of light that is superior in directivity can beobtained.

Embodiment B-4

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-2. As shown inFIG. 6, it is characterized in that a hollow 16 a for accommodatingluminous element 2 is provided on one surface (upper surface in FIG. 6)of insulating substrate 16, luminous element 2 is mounted at the bottomof hollow 16 a, and sealing part is provided inside hollow 16 a. Here,printed wirings 17 and 17, formed on insulating substrate 16, areextended to the bottom of hollow 16 a, and connected electrically toluminous layer part 21, composed of a gallium nitride semiconductor, inluminous element 2 via conductive wires 15 and 15. Meanwhile, the samecomponents as in embodiment B-2 are designated by the same referencenumerals to omit redundant explanations.

Thus, sealing part 19 of light emitting device 1B of the presentembodiment is formed by filling hollow 16 a, formed on the upper surfaceof insulating substrate 16, and therefore sealing part 19 can be formedwithout using frame 18 (see FIG. 5) described in Embodiment B-2 or themolding die described in Embodiment B-3. This advantageously simplifiesthe sealing process of luminous element 2, compared with Embodiments B-2and B-3.

Embodiment B-5

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-4. As shown inFIG. 7, it is characterized in that luminous element 2 is so-calledflip-chip-mounted on insulating substrate 16. That is, luminous element2 is provided with bumps 24 and 24, made of conductive material, on therespective surface side of the p-type semiconductor layer (not shown)and n-type semiconductor layer (not shown) in luminous layer part 21,and luminous layer part 21 is electrically connected to printed wiring17 and 17 of insulating substrate 16, with its face down, via bumps 24and 24. Accordingly, in luminous element 2 of the present embodiment,luminous layer part 21 is disposed on the side nearest to insulatingsubstrate 16, reflecting layer 23 is disposed on the side farthest frominsulating substrate 16, and phosphor part 3B is sandwiched by luminouslayer part 21 and reflecting layer 23. Meanwhile, the same components asin embodiment B-4 are designated by the same reference numerals to omitredundant explanations.

In light emitting device 1B of the present embodiment, the lightreflected by reflecting layer 23 in the downward (back) direction inFIG. 7 is then reflected by the inner circumferential surface of hollow16 a before being radiated in the upward (front) direction in FIG. 7. Inthis context, it is desirable to provide separately a reflecting layerthat is made of material whose reflectance is high, in the innercircumferential surface of hollow 16 a, except at printed wirings 17 and17.

Thus, light emitting device 1B of the present embodiment does notrequire conductive wires 15 and 15 like those in Embodiment B-4 forconnecting printed wirings 17 and 17 provided on insulating substrate 16and luminous element 2. This enables improvement in mechanical strengthand reliability, compared with Embodiment B-4.

Embodiment B-6

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-5. However, asshown in FIG. 8, it is different in that reflecting layer 23, describedin Embodiment B-5, is not provided. In other words, in light emittingdevice 1B of the present embodiment, the light emitted from luminouslayer part 21 and that emitted from phosphor part 3B are radiated in thefront direction directly after passing through sealing part 19.Meanwhile, the same components as in embodiment B-5 are designated bythe same reference numerals to omit redundant explanations.

Thus, light emitting device 1B of the present embodiment can reduce thenumber of components, compared with Embodiment B-5, which results infacilitating the manufacture thereof.

Embodiment B-7

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-1. As shown inFIG. 9, it is characterized in that mold part 11, covering luminouselement 2, is provided and mold part 11 is formed integrally with thephosphor part. Meanwhile, the same components as in Embodiment B-1 aredesignated by the same reference numerals to omit redundantexplanations.

While producing light emitting device 1B of the present embodiment, moldpart 11 is formed by a method, for example, in which a product inprogress without mold part 11 is immersed in a molding die storing aphosphor part formation liquid and the phosphor part formation liquid(polycondensation product) is cured.

Since mold part 11 and the phosphor part are integrally formed in thepresent embodiment, it becomes possible to enhance sealing properties,transparency, light resistance and heat resistance of mold part 11 andto inhibit crack generations and peelings accompanying a long-term use,by means of using the semiconductor light-emitting device member of thepresent invention as phosphor part, as described later.

Embodiment B-8

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-1. As shown inFIG. 10, it is characterized in that a cup-shaped phosphor part 3B whoserear surface is open is mounted on the outer surface of mold part 11.That is, in the present embodiment, instead of providing phosphor part3B in luminous element 2 like Embodiment B-1, phosphor part 3B in ashape along an outer circumference of mold part 11 is provided.Meanwhile, the same components as in Embodiment B-1 are designated bythe same reference numerals to omit redundant explanations.

Phosphor part 3B in the present embodiment may be formed as a thin filmby the method of curing the phosphor part formation liquid(polycondensation product) as described in Embodiment B-7. Or otherwise,it may be formed by mounting a member, which is a solid phosphor partmolded in a cup-shape in advance, on mold part 11.

Thus, in light emitting device 1B of the present embodiment, the amountof the material used for the phosphor part can be reduced, compared withthe case of light emitting device 1B of Embodiment B-7, in which thewhole mold part 11 is formed integrally with the phosphor part. And thisenables the cost reduction.

Embodiment B-9

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-2. As shown inFIG. 11, it is characterized in that a frame-shaped frame 18, encirclingluminous element 2 on one surface (upper surface in FIG. 11) ofinsulating substrate 16, is provided and sealing part 19 inside frame 18is formed of a phosphor part the same as that of phosphor part 3Bdescribed in Embodiment B-2. Meanwhile, the same components as inembodiment B-2 are designated by the same reference numerals to omitredundant explanations.

Since sealing part 19 is formed of the phosphor part in the presentembodiment, it becomes possible to enhance sealing properties,transparency, light resistance and heat resistance of sealing part 19and to inhibit crack generations and peelings accompanying a long-termuse, by means of using the semiconductor light-emitting device member ofthe present invention as phosphor part, as described later.

Embodiment B-10

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-2. As shown inFIG. 12, it is characterized in that a frame-shaped frame 18, encirclingluminous element 2 on one surface (upper surface in FIG. 12) ofinsulating substrate 16, is provided and sealing part 19 inside frame 18is formed of a phosphor part the same as that of phosphor part 3Bdescribed in Embodiment B-2. Meanwhile, the same components as inembodiment B-2 are designated by the same reference numerals to omitredundant explanations.

Since sealing part 19 is formed of the phosphor part in the presentembodiment, it becomes possible to enhance sealing properties,transparency, light resistance and heat resistance of sealing part 19and to inhibit crack generations and peelings accompanying a long-termuse, by means of using the semiconductor light-emitting device member ofthe present invention as phosphor part, as described later.

Furthermore, in the present embodiment, phosphor part 3B is formed onthe rear surface of luminous layer part 21 contained in luminous element2, and sealing part 19 covering luminous element 2 is formed of aphosphor part. This results in that the phosphor parts are present inall directions from luminous layer part 21 of luminous element 2. Thisstructure leads to the advantageous effect that excitation and lightemission of the phosphor parts can be performed more efficiently thanEmbodiment B-9.

Embodiment B-11

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-2. As shown inFIG. 13, it is characterized in that phosphor part 33 formed in advancein a lens shape is disposed on the upper surface of sealing part 19,which is made of light-transmissible material. Here, phosphor part 33 ismade of the same material as that of phosphor part 3B described inEmbodiment B-2 and is used to emit light of the desired wavelength afterbeing excited by the light from luminous element 2. Meanwhile, the samecomponents as in embodiment B-2 are designated by the same referencenumerals to omit redundant explanations.

Thus, in light emitting device 1B of the present embodiment, phosphorpart 33 performs not only function of wavelength conversion, but also ofa lens. This lens effect enables the directivity control of the lightemission.

Embodiment B-12

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-2. As shown inFIG. 14, it is characterized in that phosphor part 33 formed in advancein a lens shape is disposed on the upper surface of sealing part 19,which is made of light-transmissible material. Here, phosphor part 33 ismade of the same material as that of phosphor part 3B described inEmbodiment B-2 and is used to emit light of the desired wavelength afterbeing excited by the light from luminous element 2. Meanwhile, the samecomponents as in embodiment B-2 are designated by the same referencenumerals to omit redundant explanations.

Thus, in light emitting device 1B of the present embodiment, phosphorpart 33 performs not only function of wavelength conversion, but also ofa lens. This lens effect enables the directivity control of the lightemission. Furthermore, in the present embodiment, phosphor part 3B isformed on the rear surface of luminous layer part 21 contained inluminous element 2. This structure leads to the advantageous effect thatexcitation and light emission of the phosphor parts can be performedmore efficiently than Embodiment B-11.

Embodiment B-13

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-3. However, asshown in FIG. 15, it is characterized in that sealing part 19, coveringthe luminous element 2 and provided on the upper surface side ofinsulating substrate 16, is formed of the phosphor part. Here, sealingpart 19 of the present embodiment comprises, like Embodiment B-3, asealing function part 19 a in a truncated cone shape for sealingluminous element 2 and a lens function part 19 b in a lens shape tofunction as a lens at the front end portion of sealing part 19.Meanwhile, the same components as in Embodiment B-3 are designated bythe same reference numerals to omit redundant explanations.

Thus, in light emitting device 1B of the present embodiment, sealingpart 19 has functions of, not only sealing/protecting luminous element2, but also converting the wavelength of the light from luminous element2 and being a lens to control the directivity of light emission. Also,the weather resistance of sealing part 19 can be enhanced and thus thelifetime of light emitting device 1B can be prolonged. Furthermore, inthe present embodiment, phosphor part 3B is formed on the rear surfaceof luminous layer part 21 contained in luminous element 2, and sealingpart 19, covering luminous element 2, is formed of a phosphor part. Thisresults in that the phosphor parts are present in all directions fromluminous layer part 21 of luminous element 2. This structure leads tothe advantageous effect that excitation and light emission of thephosphor parts can be performed more efficiently than Embodiment B-12.

Embodiment B-14

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-3. However, asshown in FIG. 16, it is characterized in that sealing part 19, coveringthe luminous element 2 and provided on one surface (the upper surface inFIG. 16) side of insulating substrate 16, is formed of phosphor part 3B.Here, sealing part 19 of the present embodiment comprises, likeEmbodiment B-3, a sealing function part 19 a in a truncated cone shapefor sealing luminous element 2 and a lens function part 19 b in a lensshape to function as a lens at the front end portion of sealing part 19.Meanwhile, the same components as in Embodiment B-3 are designated bythe same reference numerals to omit redundant explanations.

Thus, in light emitting device 1B of the present embodiment, sealingpart 19 has functions of, not only sealing/protecting luminous element2, but also converting the wavelength of the light from luminous element2 and being a lens to control the directivity of light emission. Also,the weather resistance of sealing part 19 can be enhanced and thus thelifetime of light emitting device 1B can be prolonged.

Embodiment B-15

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-3. As shown inFIG. 17, it is characterized in that dome-shaped phosphor part 34covering luminous element 2 is disposed on the upper surface side ofinsulating substrate 16 and sealing part 19, made of light-transmissibleresin, is formed on the outer surface side of phosphor part 34. Here,sealing part 19 of the present embodiment comprises, like EmbodimentB-3, a sealing function part 19 a for sealing luminous element 2 and alens function part 19 b in a lens shape to function as a lens at thefront end portion of sealing part 19. Meanwhile, the same components asin Embodiment B-3 are designated by the same reference numerals to omitredundant explanations.

Thus, in light emitting device 1B of the present embodiment, the amountof the material used for phosphor part 34 can be reduced, compared withEmbodiments B-13 and B-14. In addition, since dome-shaped phosphor part34 covering luminous element 2 is disposed in the present embodiment,the degradation of luminous element 2, due to moisture from outside orthe like, can be prevented more reliably, by means of using thesemiconductor light-emitting device member of the present invention asphosphor part, as described later. This enables the lifetime of lightemitting device 1B to be prolonged.

Embodiment B-16

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-3. As shown inFIG. 18, it is characterized in that dome-shaped phosphor part 34covering luminous element 2 is disposed on the upper surface side ofinsulating substrate 16 and sealing part 19 is formed on the outersurface side of phosphor part 34. Here, sealing part 19 of the presentembodiment comprises, like Embodiment B-3, a sealing function part 19 afor sealing luminous element 2 and a lens function part 19 b in a lensshape to function as a lens at the front end portion of sealing part 19.Meanwhile, the same components as in Embodiment B-3 are designated bythe same reference numerals to omit redundant explanations.

Thus, in light emitting device 1B of the present embodiment, the amountof the material used for phosphor part 34 can be reduced, compared withEmbodiments B-13 and B-14. In addition, since dome-shaped phosphor part34 covering luminous element 2 is disposed in the present embodiment,the degradation of luminous element 2, due to moisture from outside orthe like, can be prevented more reliably, by means of using thesemiconductor light-emitting device member of the present invention asphosphor part, as described later. This enables the lifetime of lightemitting device 1B to be prolonged. Furthermore, in the presentembodiment, phosphor part 3B is formed on the rear surface of luminouslayer part 21 contained in luminous element 2, and sealing part 19,covering luminous element 2, is formed of a phosphor part. This resultsin that the phosphor parts are present in all directions from luminouslayer part 21 of luminous element 2. This structure leads to theadvantageous effect that excitation and light emission of the phosphorparts can be performed more efficiently than Embodiment B-15.

Embodiment B-17

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-4. As shown inFIG. 19, it is characterized in that sealing part 19 for sealingluminous element 2, disposed at the bottom of hollow 16 a formed on onesurface (upper surface in FIG. 19) of insulating substrate 16, isprovided and that sealing part 19 is formed of the phosphor part. Here,the phosphor part is used to emit light of the desired wavelength afterbeing excited by the light from luminous element 2, just like phosphorpart 3B described in Embodiment B-1. Meanwhile, the same components asin embodiment B-4 are designated by the same reference numerals to omitredundant explanations.

Since sealing part 19 is formed of the phosphor part in light emittingdevice 1B of the present embodiment, it becomes possible to enhancesealing properties, transparency, light resistance and heat resistanceof sealing part 19 and to inhibit crack generations and peelingsaccompanying a long-term use, by means of using the semiconductorlight-emitting device member of the present invention as phosphor part,as described later. Furthermore, in the present embodiment, phosphorpart 3B is formed on the rear surface of luminous layer part 21contained in luminous element 2, and sealing part 19, covering luminouselement 2, is formed of a phosphor part 3B. This results in that thephosphor parts are present in all directions from luminous layer part 21of luminous element 2. This structure leads to the advantageous effectthat excitation and light emission of the phosphor parts can beperformed more efficiently than Embodiment B-15.

Embodiment B-18

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-4. As shown inFIG. 20, it is characterized in that sealing part 19 for sealingluminous element 2, disposed at the bottom of hollow 16 a formed on onesurface (upper surface in FIG. 20) of insulating substrate 16, isprovided and that sealing part 19 is formed of the phosphor part 3B.Here, that phosphor part 3B is used to emit light of the desiredwavelength after being excited by the light from luminous element 2,just like phosphor part 3B described in Embodiment B-1. Meanwhile, thesame components as in embodiment B-4 are designated by the samereference numerals to omit redundant explanations.

Since sealing part 19 is formed of the phosphor part in light emittingdevice 1B of the present embodiment, it becomes possible to enhancesealing properties, transparency, light resistance and heat resistanceof sealing part 19 and to inhibit crack generations and peelingsaccompanying a long-term use, by means of using the semiconductorlight-emitting device member of the present invention as phosphor part3B, as described later.

Embodiment B-19

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-4. As shown inFIG. 21, it is characterized in that phosphor part 33 formed in a lensshape in advance is disposed on the upper surface (which is, the lightextraction surface) of sealing part 19. Here, that phosphor part 33 isused to emit light of the desired wavelength after being excited by thelight from luminous element 2, just like phosphor part 3B described inEmbodiment B-1. Meanwhile, the same components as in embodiment B-4 aredesignated by the same reference numerals to omit redundantexplanations.

Thus, in light emitting device 1B of the present embodiment, phosphorpart 33 performs not only function of wavelength conversion, but also ofa lens. This lens effect enables the directivity control of the lightemission.

Embodiment B-20

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-4. As shown inFIG. 22, it is characterized in that phosphor part 33 formed in a lensshape in advance is disposed on the upper surface (which is, the lightextraction surface) of sealing part 19. Here, that phosphor part 33 isused to emit light of the desired wavelength after being excited by thelight from luminous element 2, just like phosphor part 3B described inEmbodiment B-1. Meanwhile, the same components as in embodiment B-4 aredesignated by the same reference numerals to omit redundantexplanations.

Thus, in light emitting device 1B of the present embodiment, phosphorpart 33 performs not only function of wavelength conversion, but also ofa lens. This lens effect enables the directivity control of the lightemission. Furthermore, in the present embodiment, since phosphor part 3Bis formed also on the rear surface of luminous layer part 21 containedin luminous element 2, the excitation and light emission of the phosphorpart is performed more efficiently than Embodiment B-19.

Embodiment B-21

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-5. As shown inFIG. 23, it is characterized in that sealing part 19 for sealingluminous element 2 disposed at the bottom of hollow 16 a formed on onesurface (upper surface in FIG. 23) of insulating substrate 16 isprovided and that sealing part 19 is formed of phosphor part 3B. Sealingpart 19 is, as shown in FIG. 24, inserted into hollow 16 a of insulatingsubstrate 16 on which luminous element 2 is mounted, after it isprocessed in advance to have the outer circumferential, the shape ofwhich corresponds to hollow 16 a, and a recess 19 c, at a positioncorresponding to luminous element 2, for accommodating luminous element2. This structure enables the sealing process to be simplified. Here,phosphor part 3B, constituting sealing part 19, is used to emit light ofthe desired wavelength after being excited by the light from luminouselement 2, just like phosphor part 3B described in Embodiment B-1.Meanwhile, the same components as in embodiment B-5 are designated bythe same reference numerals to omit redundant explanations.

Since sealing part 19 is formed of the phosphor part in light emittingdevice 1B of the present embodiment, it becomes possible to enhancesealing properties, transparency, light resistance and heat resistanceof sealing part 19 and to inhibit crack generations and peelingsaccompanying a long-term use, by means of using the semiconductorlight-emitting device member of the present invention as phosphor part3B, as described later. In addition, in the present embodiment, lightemitted in the front direction from luminous layer part 21 of luminouselement 2 is once reflected by reflecting layer 23 toward the innerbottom surface of hollow 16 a. Therefore, if reflecting layers areprovided on the inner bottom surface and inner circumferential surfaceof hollow 16 a, the reflected light will be reflected further by thatinner bottom surface and inner circumferential surface, before beingradiated in the front direction. With this structure, length of theoptical path can be extended, and therefore, the advantageous effect ofmore efficient excitation and light emission by phosphor part 3B can berealized.

Embodiment B-22

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-5. As shown inFIG. 25, it is characterized in that sealing part 19 for sealingluminous element 2 disposed at the bottom of hollow 16 a formed on onesurface (upper surface in FIG. 25) of insulating substrate 16 isprovided and that sealing part 19 is formed of phosphor part 3B. Sealingpart 19 is, as shown in FIG. 26, inserted into hollow 16 a of insulatingsubstrate 16 on which luminous element 2 is mounted, after it isprocessed in advance to have the outer circumferential, the shape ofwhich corresponds to hollow 16 a, and a recess 19 c, at a positioncorresponding to luminous element 2, for accommodating luminous element2. This structure enables the sealing process to be simplified. Here,phosphor part 3B, constituting sealing part 19, is used to emit light ofthe desired wavelength after being excited by the light from luminouselement 2, just like phosphor part 3B described in Embodiment B-1.Meanwhile, the same components as in embodiment B-5 are designated bythe same reference numerals to omit redundant explanations.

Since sealing part 19 is formed of phosphor part 3B in light emittingdevice 1B of the present embodiment, it becomes possible to enhancesealing properties, transparency, light resistance and heat resistanceof sealing part 19 and to inhibit crack generations and peelingsaccompanying a long-term use, by means of using the semiconductorlight-emitting device member of the present invention as phosphor part3B, as described later.

Embodiment B-23

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-6. As shown inFIG. 27, it is characterized in that phosphor part 3B that is processedlike a rod in advance is disposed on the upper surface of luminouselement 2. Around luminous element 2 and phosphor part 3B, sealing part19, made of light-transmissible material, is formed. As regards phosphorpart 3B, one end surface (lower end surface in FIG. 27) thereof is inclose contact with luminous layer part 21 of luminous element 2, andanother end surface (upper end surface in FIG. 27) thereof is exposed.Meanwhile, the same components as in Embodiment B-6 are designated bythe same reference numerals to omit redundant explanations.

Thus, in light emitting device 1B of the present embodiment, sincephosphor part 3B, whose one end surface is in close contact withluminous layer part 21 of luminous element 2, is formed like a rod, thelight emitted from luminous layer part 21 can be absorbed efficientlyinto phosphor part 3B through the one end surface of phosphor part 3B.Then phosphor part 3B emits light, when excited by the absorbed light,to the outside efficiently through another end surface described above,of phosphor part 3B. In the present embodiment, only one phosphor part3B, formed to be like a rod having a relatively large diameter, is used.Or otherwise, a plurality of phosphor parts 3B, formed to be like abundle of fibers having relatively small diameters respectively, can bedisposed, as shown in FIG. 28. In addition, the sectional shape ofphosphor part 3B is not limited to a round shape, but may be, forexample, a quadrangular shape, or other.

Embodiment B-24

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-23. As shown inFIG. 29, it is characterized in that the sealing part 19, providedinside hollow 16 a of insulating substrate 16, is provided and thatsealing part 19 is formed of phosphor part 3B. Sealing part 19 is, asshown in FIG. 30, inserted into hollow 16 a of insulating substrate 16on which luminous element 2 is mounted, after it is processed in advanceto have outer circumferential, the shape of which corresponds to hollow16 a, and a through-hole 19 d, at a position corresponding to luminouselement 2, for accommodating luminous element 2. This structure enablesthe sealing process to be simplified. Here, phosphor part 3B,constituting sealing part 19, is used to emit light of the desiredwavelength after being excited by the light from luminous element 2,just like phosphor part 3B described in Embodiment B-1. Meanwhile, thesame components as in Embodiment B-23 are designated by the samereference numerals to omit redundant explanations.

Thus, in light emitting device 1B of the present embodiment, sincesealing part 19 is also formed of phosphor part 3B, it becomes possibleto prolong the lifetime of light emitting device 1B and enhance inefficiency of the light emission. Though, in the present embodiment,only one phosphor part 3B, formed to be like a rod having a relativelylarge diameter, is used, a plurality of phosphor parts 3B, formed to belike a bundle of fibers having relatively small diameters, can bedisposed, as shown in FIG. 31. In addition, the sectional shape ofphosphor part 3B is not limited to a round shape, but may be, forexample, a quadrangular shape, or other.

Embodiment B-25

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-2. As shown inFIG. 32, it is characterized in that frame 18 is disposed on one surface(the upper surface in FIG. 32) of insulating substrate 16, luminouslayer part 21 in luminous element 2 is based on AlGaN and emits nearultraviolet light, and phosphor powder (for example, powder of aYAG:Ce³⁺ phosphor emitting yellow light after being excited by nearultraviolet light) is dispersed in a light-transmissible material whichis used as sealing part 19 disposed inside frame 18. In the presentembodiment, fluorophosphate glass (for example,P₂O₅.AlF₃.MgF.CaF₂.SrF₂.BaCl₂:Eu²⁺ emitting blue light after beingexcited by near ultraviolet light) is used as phosphor part 3B.Meanwhile, the same components as in embodiment B-2 are designated bythe same reference numerals to omit redundant explanations.

Thus, in light emitting device 1B of the present embodiment, since aphosphor powder that emits light after being excited by the light fromluminous element 2 is dispersed in sealing part 19, light output of alight synthesized from the light emitted from luminous element 2, thelight emitted from phosphor part 3B and the light emitted from thephosphor powder is obtained.

Consequently, by selecting material that emits near ultraviolet light asmaterial of luminous layer part 21 in luminous element 2, both phosphorpart 3B and the phosphor powder in sealing part 19 will be excited bythe light emitted from luminous element 2 and emit lights intrinsic toeach of them. And a synthesized light can be obtained from those lights.In the present embodiment, a blue light is emitted from phosphor part 3Band a yellow light is emitted from the phosphor powder, so as to obtaina white light, which is different from both luminescent colors.

Light-emitting materials for existing phosphor particles in the phosphorpart or for existing phosphor powders are limited, and thereforesometimes the desired light color may not be obtainable by using eitherthe phosphor powder or phosphor part. The present embodiment is veryeffective in such a case. That is, even if the desired characteristicsof light color cannot be obtained from phosphor part 3B alone, lightemitting device 1B of the desired characteristics of light color can berealized just by using a phosphor powder having suitable, complementarylight-color characteristics, which lacks in phosphor part 3B. Inaddition, the luminescent color of the phosphor powder can be setidentical to that of phosphor part 3B, differently from the case in thepresent embodiment. With that configuration, it becomes possible toincrease the light output and enhance the emission efficiency becausethe light emitted from the phosphor powder is superimposed on the lightemitted from phosphor part 3B. In this context, when the luminescentcolors of phosphor part 3B and the phosphor powder are set to beapproximately identical, by using P₂O₅.SrF₂.BaF₂:Eu³⁺ and Y₂O₂S:Eu³⁺,both emitting red light, as phosphor particles of phosphor part 3B andthe phosphor powder respectively, an efficient red emission light can beobtained. This combination of phosphor part 3B and the phosphor powderis only an example, and any other combination may naturally be adopted.

Embodiment B-26

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-3. As shown inFIG. 33, it is characterized in that sealing part 19 for sealingluminous element 2 from one side (the upper side in FIG. 33) ofinsulating substrate 16 is provided, luminous layer part 21 in luminouselement 2 is based on AlGaN and emits near ultraviolet light, andphosphor powder (for example, powder of a YAG:Ce³⁺ phosphor emittingyellow light after being excited by near ultraviolet light) is dispersedin a light-transmissible material which is used as sealing part 19, andsealing part 19 functions as a phosphor part. In the present embodiment,fluorophosphate glass (for example, P₂O₅.AlF₃.MgF.CaF₂.SrF₂.BaCl₂:Eu²⁺emitting blue light after being excited by near ultraviolet light) isused as phosphor particles in phosphor part 3B. Meanwhile, the samecomponents as in Embodiment B-3 are designated by the same referencenumerals to omit redundant explanations.

Thus, in light emitting device 1B of the present embodiment, just as inEmbodiment B-25, since a phosphor powder that emits light after beingexcited by the light from luminous element 2 is dispersed in sealingpart 19, light output of a light synthesized from the light emitted fromluminous element 2, the light emitted from phosphor part 3B and thelight emitted from the phosphor powder is obtained. Consequently, justas in Embodiment B-25, by selecting material that emits near ultravioletlight as material of luminous layer part 21 in luminous element 2, bothphosphor part 3B and the phosphor powder in sealing part 19 will beexcited by the light emitted from luminous element 2 and emit lightsintrinsic to each of them. And a synthesized light can be obtained fromthose lights. In addition, the luminescent color of the phosphor powdercan be set identical to that of phosphor part 3B, differently from thecase in the present embodiment. With that configuration, it becomespossible to increase the light output and enhance the emissionefficiency because the light emitted from the phosphor powder issuperimposed on the light emitted from phosphor part 3B.

Embodiment B-27

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-4. As shown inFIG. 34, it is characterized in that sealing part 19 for sealingluminous element 2 by filling up hollow 16 a formed on the upper surfaceof insulating substrate 16 is provided, luminous layer part 21 inluminous element 2 is based on AlGaN and emits near ultraviolet light,and phosphor powder (for example, powder of a YAG:Ce³⁺ phosphor emittingyellow light after being excited by near ultraviolet light) is dispersedin a light-transmissible material which is used as sealing part 19, andsealing part 19 functions as a phosphor part. In the present embodiment,fluorophosphate glass (for example, P₂O₅.AlF₃.MgF.CaF₂.SrF₂.BaCl₂:Eu²⁺emitting blue light after being excited by near ultraviolet light) isused as phosphor particles in phosphor part 3B. Meanwhile, the samecomponents as in embodiment B-4 are designated by the same referencenumerals to omit redundant explanations.

Thus, in light emitting device 1B of the present embodiment, just as inEmbodiment B-25, since a phosphor powder that emits light after beingexcited by the light from luminous element 2 is dispersed in sealingpart 19, light output of a light synthesized from the light emitted fromluminous element 2, the light emitted from phosphor part 3B and thelight emitted from the phosphor powder is obtained. Consequently, justas in Embodiment B-25, by selecting material that emits near ultravioletlight as material of luminous layer part 21 in luminous element 2, bothphosphor part 3B and the phosphor powder in sealing part 19 will beexcited by the light emitted from luminous element 2 and emit lightsintrinsic to each of them. And a synthesized light can be obtained fromthose lights. In addition, the luminescent color of the phosphor powdercan be set identical to that of phosphor part 3B, differently from thecase in the present embodiment. With that configuration, it becomespossible to increase the light output and enhance the emissionefficiency because the light emitted from the phosphor powder issuperimposed on the light emitted from phosphor part 3B.

Embodiment B-28

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-5. As shown inFIG. 35, it is characterized in that sealing part 19 for sealingluminous element 2 by filling up hollow 16 a formed on one surface (theupper surface in FIG. 35) of insulating substrate 16 is provided,luminous layer part 21 in luminous element 2 is based on AlGaN and emitsnear ultraviolet light, and phosphor powder (for example, powder of aYAG:Ce³⁺ phosphor emitting yellow light after being excited by nearultraviolet light) is dispersed in a light-transmissible material whichis used as sealing part 19, and sealing part 19 functions as a phosphorpart. In the present embodiment, fluorophosphate glass (for example,P₂O₅.AlF₃.MgF.CaF₂.SrF₂.BaCl₂:Eu²⁺ emitting blue light after beingexcited by near ultraviolet light) is used as phosphor particles inphosphor part 3B. Meanwhile, the same components as in embodiment B-5are designated by the same reference numerals to omit redundantexplanations.

Thus, in light emitting device 1B of the present embodiment, just as inEmbodiment B-25, since a phosphor powder that emits light after beingexcited by the light from luminous element 2 is dispersed in sealingpart 19, light output of a light synthesized from the light emitted fromluminous element 2, the light emitted from phosphor part 3B and thelight emitted from the phosphor powder is obtained. Consequently, justas in Embodiment B-25, by selecting material that emits near ultravioletlight as material of luminous layer part 21 in luminous element 2, bothphosphor part 3B and the phosphor powder in sealing part 19 will beexcited by the light emitted from luminous element 2 and emit lightsintrinsic to each of them. And a synthesized light can be obtained fromthose lights. In addition, the luminescent color of the phosphor powdercan be set identical to that of phosphor part 3B, differently from thecase in the present embodiment. With that configuration, it becomespossible to increase the light output and enhance the emissionefficiency because the light emitted from the phosphor powder issuperimposed on the light emitted from phosphor part 3B.

Embodiment B-29

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-6. As shown inFIG. 36, it is characterized in that sealing part 19 for sealingluminous element 2 by filling up hollow 16 a formed on one surface (theupper surface in FIG. 36) of insulating substrate 16 is provided,luminous layer part 21 in luminous element 2 is based on AlGaN and emitsnear ultraviolet light, and phosphor powder (for example, powder of aYAG:Ce³⁺ phosphor emitting yellow light after being excited by nearultraviolet light) is dispersed in a light-transmissible material whichis used as sealing part 19, and sealing part 19 functions as a phosphorpart. In the present embodiment, fluorophosphate glass (for example,P₂O₅.AlF₃.MgF.CaF₂.SrF₂.BaCl₂:Eu²⁺ emitting blue light after beingexcited by near ultraviolet light) is used as phosphor particles inphosphor part 3B. Meanwhile, the same components as in Embodiment B-6are designated by the same reference numerals to omit redundantexplanations.

Thus, in light emitting device 1B of the present embodiment, just as inEmbodiment B-25, since a phosphor powder that emits light after beingexcited by the light from luminous element 2 is dispersed in sealingpart 19, light output of a light synthesized from the light emitted fromluminous element 2, the light emitted from phosphor part 3B and thelight emitted from the phosphor powder is obtained. Consequently, justas in Embodiment B-25, by selecting material that emits near ultravioletlight as material of luminous layer part 21 in luminous element 2, bothphosphor part 3B and the phosphor powder in sealing part 19 will beexcited by the light emitted from luminous element 2 and emit lightsintrinsic to each of them. And a synthesized light can be obtained fromthose lights. In addition, the luminescent color of the phosphor powdercan be set identical to that of phosphor part 3B, differently from thecase in the present embodiment. With that configuration, it becomespossible to increase the light output and enhance the emissionefficiency because the light emitted from the phosphor powder issuperimposed on the light emitted from phosphor part 3B.

Embodiment B-30

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-1. As shown inFIG. 37( a) and FIG. 37( b), it is characterized in that the shell typeshape mold part is provided, luminous layer part 21 in luminous element2 is based on AlGaN and emits near ultraviolet light, and phosphorpowder (for example, powder of a YAG:Ce³⁺ phosphor emitting yellow lightafter being excited by near ultraviolet light) is dispersed in alight-transmissible material which is used as mold part 11, and moldpart 11 functions as a phosphor part. In the present embodiment,fluorophosphate glass (for example, P₂O₅.AlF₃.MgF.CaF₂.SrF₂.BaCl₂:Eu²⁺emitting blue light after being excited by near ultraviolet light) isused as phosphor particles in phosphor part 3B. Meanwhile, the samecomponents as in Embodiment B-1 are designated by the same referencenumerals to omit redundant explanations.

Thus, in light emitting device 1B of the present embodiment, just as inEmbodiment B-25, since a phosphor powder that emits light after beingexcited by the light from luminous element 2 is dispersed in mold part11, light output of a light synthesized from the light emitted fromluminous element 2, the light emitted from phosphor part 3B and thelight emitted from the phosphor powder is obtained. Consequently, justas in Embodiment B-25, by selecting material that emits near ultravioletlight as material of luminous layer part 21 in luminous element 2, bothphosphor part 3B and the phosphor powder in mold part 11 will be excitedby the light emitted from luminous element 2 and emit lights intrinsicto each of them. And a synthesized light can be obtained from thoselights. In addition, the luminescent color of the phosphor powder can beset identical to that of phosphor part 3B, differently from the case inthe present embodiment. With that configuration, it becomes possible toincrease the light output and enhance the emission efficiency becausethe light emitted from the phosphor powder is superimposed on the lightemitted from phosphor part 3B.

Embodiment B-31

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-8. As shown inFIG. 38, it is characterized in that the shell type shape mold part 11is provided, luminous layer part 21 (not shown in FIG. 38) in luminouselement 2 is based on AlGaN and emits near ultraviolet light, andphosphor powder (for example, powder of a YAG:Ce³⁺ phosphor emittingyellow light after being excited by near ultraviolet light) is dispersedin a light-transmissible material which is used as mold part 11, andmold part 11 functions as a phosphor part. In the present embodiment,fluorophosphate glass (for example, P₂O₅.AlF₃.MgF.CaF₂.SrF₂.BaCl₂:Eu²⁺emitting blue light after being excited by near ultraviolet light) isused as phosphor particles in phosphor part 3B. Meanwhile, the samecomponents as in Embodiment B-8 are designated by the same referencenumerals to omit redundant explanations.

Thus, in light emitting device 1B of the present embodiment, just as inEmbodiment B-25, since a phosphor powder that emits light after beingexcited by the light from luminous element 2 is dispersed in mold part11, light output of a light synthesized from the light emitted fromluminous element 2, the light emitted from phosphor part 3B and thelight emitted from the phosphor powder is obtained. Consequently, justas in Embodiment B-25, by selecting material that emits near ultravioletlight as material of luminous layer part 21 in luminous element 2, bothphosphor part 3B and the phosphor powder in mold part 11 will be excitedby the light emitted from luminous element 2 and emit lights intrinsicto each of them. And a synthesized light can be obtained from thoselights. In addition, the luminescent color of the phosphor powder can beset identical to that of phosphor part 3B, differently from the case inthe present embodiment. With that configuration, it becomes possible toincrease the light output and enhance the emission efficiency becausethe light emitted from the phosphor powder is superimposed on the lightemitted from phosphor part 3B.

Embodiment B-32

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-11. As shown inFIG. 39, it is characterized in that sealing part 19 for sealingluminous element 2 from one side (the upper side in FIG. 39) ofinsulating substrate is provided, luminous layer part 21 in luminouselement 2 is based on AlGaN and emits near ultraviolet light, andphosphor powder (for example, powder of a YAG:Ce³⁺ phosphor emittingyellow light after being excited by near ultraviolet light) is dispersedin a light-transmissible material which is used as sealing part 19, andsealing part 19 functions as a phosphor part. In the present embodiment,fluorophosphate glass (for example, P₂O₅.AlF₃.MgF.CaF₂.SrF₂.BaCl₂:Eu²⁺emitting blue light after being excited by near ultraviolet light) isused as phosphor particles in phosphor part 33. Meanwhile, the samecomponents as in Embodiment B-11 are designated by the same referencenumerals to omit redundant explanations.

Thus, in light emitting device 1B of the present embodiment, just as inEmbodiment B-25, since a phosphor powder that emits light after beingexcited by the light from luminous element 2 is dispersed in sealingpart 19, light output of a light synthesized from the light emitted fromluminous element 2, the light emitted from phosphor part 33 and thelight emitted from the phosphor powder is obtained. Consequently, justas in Embodiment B-25, by selecting material that emits near ultravioletlight as material of luminous layer part 21 in luminous element 2, bothphosphor part 33 and the phosphor powder in sealing part 19 will beexcited by the light emitted from luminous element 2 and emit lightsintrinsic to each of them. And a synthesized light can be obtained fromthose lights. In addition, the luminescent color of the phosphor powdercan be set identical to that of phosphor part 33, differently from thecase in the present embodiment. With that configuration, it becomespossible to increase the light output and enhance the emissionefficiency because the light emitted from the phosphor powder issuperimposed on the light emitted from phosphor part 33.

Embodiment B-33

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-15. As shown inFIG. 40, it is characterized in that sealing part 19 for sealingluminous element 2 from one side (the upper side in FIG. 40) ofinsulating substrate 16 is provided, luminous layer part 21 in luminouselement 2 is based on AlGaN and emits near ultraviolet light, andphosphor powder (for example, powder of a YAG:Ce³⁺ phosphor emittingyellow light after being excited by near ultraviolet light) is dispersedin a light-transmissible material which is used as sealing part 19, andsealing part 19 functions as a phosphor part. In the present embodiment,fluorophosphate glass (for example, P₂O₅.AlF₃.MgF.CaF₂.SrF₂.BaCl₂:Eu²⁺emitting blue light after being excited by near ultraviolet light) isused as phosphor particles in phosphor part 34. Meanwhile, the samecomponents as in embodiment B-15 are designated by the same referencenumerals to omit redundant explanations.

Thus, in light emitting device 1B of the present embodiment, just as inEmbodiment B-25, since a phosphor powder that emits light after beingexcited by the light from luminous element 2 is dispersed in sealingpart 19, light output of a light synthesized from the light emitted fromluminous element 2, the light emitted from phosphor part 34 and thelight emitted from the phosphor powder is obtained. Consequently, justas in Embodiment B-25, by selecting material that emits near ultravioletlight as material of luminous layer part 21 in luminous element 2, bothphosphor part 34 and the phosphor powder in sealing part 19 will beexcited by the light emitted from luminous element 2 and emit lightsintrinsic to each of them. And a synthesized light can be obtained fromthose lights. In addition, the luminescent color of the phosphor powdercan be set identical to that of phosphor part 34, differently from thecase in the present embodiment. With that configuration, it becomespossible to increase the light output and enhance the emissionefficiency because the light emitted from the phosphor powder issuperimposed on the light emitted from phosphor part 34.

Embodiment B-34

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-19. As shown inFIG. 41, it is characterized in that sealing part 19 for sealingluminous element 2 by filling up hollow 16 a formed on one surface (theupper surface in FIG. 41) of insulating substrate 16 is provided,luminous layer part 21 in luminous element 2 is based on AlGaN and emitsnear ultraviolet light, and phosphor powder (for example, powder of aYAG:Ce³⁺ phosphor emitting yellow light after being excited by nearultraviolet light) is dispersed in a light-transmissible material whichis used as sealing part 19, and sealing part 19 functions as a phosphorpart. In the present embodiment, fluorophosphate glass (for example,P₂O₅.AlF₃.MgF.CaF₂.SrF₂.BaCl₂:Eu²⁺ emitting blue light after beingexcited by near ultraviolet light) is used as phosphor particles inphosphor part 33. Meanwhile, the same components as in embodiment B-19are designated by the same reference numerals to omit redundantexplanations.

Thus, in light emitting device 1B of the present embodiment, just as inEmbodiment B-25, since a phosphor powder that emits light after beingexcited by the light from luminous element 2 is dispersed in sealingpart 19, light output of a light synthesized from the light emitted fromluminous element 2, the light emitted from phosphor part 33 and thelight emitted from the phosphor powder is obtained. Consequently, justas in Embodiment B-25, by selecting material that emits near ultravioletlight as material of luminous layer part 21 in luminous element 2, bothphosphor part 33 and the phosphor powder in sealing part 19 will beexcited by the light emitted from luminous element 2 and emit lightsintrinsic to each of them. And a synthesized light can be obtained fromthose lights. In addition, the luminescent color of the phosphor powdercan be set identical to that of phosphor part 33, differently from thecase in the present embodiment. With that configuration, it becomespossible to increase the light output and enhance the emissionefficiency because the light emitted from the phosphor powder issuperimposed on the light emitted from phosphor part 33.

Embodiment B-35

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiments B-12 and B-22. Asshown in FIG. 42, it is characterized in that sealing part 19 forsealing luminous element 2 by filling up hollow 16 a formed on onesurface (the upper surface in FIG. 42) of insulating substrate 16 isprovided, luminous layer part 21 in luminous element 2 is based on AlGaNand emits near ultraviolet light, and phosphor powder (for example,powder of a YAG:Ce³⁺ phosphor emitting yellow light after being excitedby near ultraviolet light) is dispersed in a light-transmissiblematerial which is used as sealing part 19, and sealing part 19 functionsas a phosphor part. In the present embodiment, fluorophosphate glass(for example, P₂O₅.AlF₃.MgF.CaF₂.SrF₂.BaCl₂:Eu²⁺ emitting blue lightafter being excited by near ultraviolet light) is used as phosphorparticles in phosphor part 33. Meanwhile, the same components as inEmbodiments B-12 and B-22 are designated by the same reference numeralsto omit redundant explanations.

Thus, in light emitting device 1B of the present embodiment, just as inEmbodiment B-25, since a phosphor powder that emits light after beingexcited by the light from luminous element 2 is dispersed in sealingpart 19, light output of a light synthesized from the light emitted fromluminous element 2, the light emitted from phosphor part 33 and thelight emitted from the phosphor powder is obtained. Consequently, justas in Embodiment B-25, by selecting material that emits near ultravioletlight as material of luminous layer part 21 in luminous element 2, bothphosphor part 33 and the phosphor powder in sealing part 19 will beexcited by the light emitted from luminous element 2 and emit lightsintrinsic to each of them. And a synthesized light can be obtained fromthose lights. In addition, the luminescent color of the phosphor powdercan be set identical to that of phosphor part 33, differently from thecase in the present embodiment. With that configuration, it becomespossible to increase the light output and enhance the emissionefficiency because the light emitted from the phosphor powder issuperimposed on the light emitted from phosphor part 33.

Embodiment B-36

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-12. As shown inFIG. 43, it is characterized in that sealing part 19 for sealingluminous element 2 from one side (the upper side in FIG. 43) ofinsulating substrate 16 is provided, luminous layer part 21 in luminouselement 2 is based on AlGaN and emits near ultraviolet light, andphosphor powder (for example, powder of a YAG:Ce³⁺ phosphor emittingyellow light after being excited by near ultraviolet light) is dispersedin a light-transmissible material which is used as sealing part 19, andsealing part 19 functions as a phosphor part. In the present embodiment,fluorophosphate glass (for example, P₂O₅.AlF₃.MgF.CaF₂.SrF₂.BaCl₂:Eu²⁺emitting blue light after being excited by near ultraviolet light) isused as phosphor particles in phosphor part 3B. Meanwhile, the samecomponents as in embodiment B-12 are designated by the same referencenumerals to omit redundant explanations.

Thus, in light emitting device 1B of the present embodiment, just as inEmbodiment B-25, since a phosphor powder that emits light after beingexcited by the light from luminous element 2 is dispersed in sealingpart 19, light output of a light synthesized from the light emitted fromluminous element 2, the light emitted from phosphor part 3B and thelight emitted from the phosphor powder is obtained. Consequently, justas in Embodiment B-25, by selecting material that emits near ultravioletlight as material of luminous layer part 21 in luminous element 2, bothphosphor part 3B and the phosphor powder in sealing part 19 will beexcited by the light emitted from luminous element 2 and emit lightsintrinsic to each of them. And a synthesized light can be obtained fromthose lights. In addition, the luminescent color of the phosphor powdercan be set identical to that of phosphor part 3B, differently from thecase in the present embodiment. With that configuration, it becomespossible to increase the light output and enhance the emissionefficiency because the light emitted from the phosphor powder issuperimposed on the light emitted from phosphor part 3B.

Embodiment B-37

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-16. As shown inFIG. 44, it is characterized in that sealing part 19 for sealingluminous element 2 from one side (the upper side in FIG. 44) ofinsulating substrate 16 is provided, luminous layer part 21 in luminouselement 2 is based on AlGaN and emits near ultraviolet light, andphosphor powder (for example, powder of a YAG:Ce³⁺ phosphor emittingyellow light after being excited by near ultraviolet light) is dispersedin a light-transmissible material which is used as sealing part 19, andsealing part 19 functions as a phosphor part. In the present embodiment,fluorophosphate glass (for example, P₂O₅.AlF₃.MgF.CaF₂.SrF₂.BaCl₂:Eu²⁺emitting blue light after being excited by near ultraviolet light) isused as phosphor particles in phosphor part 34. Meanwhile, the samecomponents as in Embodiment B-16 are designated by the same referencenumerals to omit redundant explanations.

Thus, in light emitting device 1B of the present embodiment, just as inEmbodiment B-25, since a phosphor powder that emits light after beingexcited by the light from luminous element 2 is dispersed in sealingpart 19, light output of a light synthesized from the light emitted fromluminous element 2, the light emitted from phosphor part 34 and thelight emitted from the phosphor powder is obtained. Consequently, justas in Embodiment B-25, by selecting material that emits near ultravioletlight as material of luminous layer part 21 in luminous element 2, bothphosphor part 34 and the phosphor powder in sealing part 19 will beexcited by the light emitted from luminous element 2 and emit lightsintrinsic to each of them. And a synthesized light can be obtained fromthose lights. In addition, the luminescent color of the phosphor powdercan be set identical to that of phosphor part 34, differently from thecase in the present embodiment. With that configuration, it becomespossible to increase the light output and enhance the emissionefficiency because the light emitted from the phosphor powder issuperimposed on the light emitted from phosphor part 34.

Embodiment B-38

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-20. As shown inFIG. 45, it is characterized in that sealing part 19 for sealingluminous element 2 by filling up hollow 16 a formed on one surface (theupper surface in FIG. 45) of insulating substrate 16 is provided,luminous layer part 21 in luminous element 2 is based on AlGaN and emitsnear ultraviolet light, and phosphor powder (for example, powder of aYAG:Ce³⁺ phosphor emitting yellow light after being excited by nearultraviolet light) is dispersed in a light-transmissible material whichis used as sealing part 19, and sealing part 19 functions as a phosphorpart. In the present embodiment, fluorophosphate glass (for example,P₂O₅.AlF₃.MgF.CaF₂.SrF₂.BaCl₂:Eu²⁺ emitting blue light after beingexcited by near ultraviolet light) is used as phosphor particles inphosphor part 3B. Meanwhile, the same components as in Embodiment B-20are designated by the same reference numerals to omit redundantexplanations.

Thus, in light emitting device 1B of the present embodiment, just as inEmbodiment B-25, since a phosphor powder that emits light after beingexcited by the light from luminous element 2 is dispersed in sealingpart 19, light output of a light synthesized from the light emitted fromluminous element 2, the light emitted from phosphor part 3B and thelight emitted from the phosphor powder is obtained. Consequently, justas in Embodiment B-25, by selecting material that emits near ultravioletlight as material of luminous layer part 21 in luminous element 2, bothphosphor part 3B and the phosphor powder in sealing part 19 will beexcited by the light emitted from luminous element 2 and emit lightsintrinsic to each of them. And a synthesized light can be obtained fromthose lights. In addition, the luminescent color of the phosphor powdercan be set identical to that of phosphor part 3B, differently from thecase in the present embodiment. With that configuration, it becomespossible to increase the light output and enhance the emissionefficiency because the light emitted from the phosphor powder issuperimposed on the light emitted from phosphor part 3B.

Embodiment B-39

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiments B-5 and B-12. Asshown in FIG. 46, it is characterized in that sealing part 19 forsealing luminous element 2 by filling up hollow 16 a formed on onesurface (the upper surface in FIG. 46) of insulating substrate 16 isprovided, luminous layer part 21 in luminous element 2 is based on AlGaNand emits near ultraviolet light, and phosphor powder (for example,powder of a YAG:Ce³⁺ phosphor emitting yellow light after being excitedby near ultraviolet light) is dispersed in a light-transmissiblematerial which is used as sealing part 19, and sealing part 19 functionsas a phosphor part. In the present embodiment, fluorophosphate glass(for example, P₂O₅.AlF₃.MgF.CaF₂.SrF₂.BaCl₂:Eu²⁺ emitting blue lightafter being excited by near ultraviolet light) is used as phosphorparticles in phosphor part 3B. Meanwhile, the same components as inEmbodiments B-5 and B-12 are designated by the same reference numeralsto omit redundant explanations.

Thus, in light emitting device 1B of the present embodiment, just as inEmbodiment B-25, since a phosphor powder that emits light after beingexcited by the light from luminous element 2 is dispersed in sealingpart 19, light output of a light synthesized from the light emitted fromluminous element 2, the light emitted from phosphor part 3B and thelight emitted from the phosphor powder is obtained. Consequently, justas in Embodiment B-25, by selecting material that emits near ultravioletlight as material of luminous layer part 21 in luminous element 2, bothphosphor part 3B and the phosphor powder in sealing part 19 will beexcited by the light emitted from luminous element 2 and emit lightsintrinsic to each of them. And a synthesized light can be obtained fromthose lights. In addition, the luminescent color of the phosphor powdercan be set identical to that of phosphor part 3B, differently from thecase in the present embodiment. With that configuration, it becomespossible to increase the light output and enhance the emissionefficiency because the light emitted from the phosphor powder issuperimposed on the light emitted from phosphor part 3B.

Embodiment B-40

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiments B-20 and B-21. Asshown in FIG. 47, it is characterized in that sealing part 19 forsealing luminous element 2 by filling up hollow 16 a formed on onesurface (the upper surface in FIG. 47) of insulating substrate 16 isprovided, luminous layer part 21 in luminous element 2 is based on AlGaNand emits near ultraviolet light, and phosphor powder (for example,powder of a YAG:Ce³⁺ phosphor emitting yellow light after being excitedby near ultraviolet light) is dispersed in a light-transmissiblematerial which is used as sealing part 19, and sealing part 19 functionsas a phosphor part. In the present embodiment, fluorophosphate glass(for example, P₂O₅.AlF₃.MgF.CaF₂.SrF₂.BaCl₂:Eu²⁺ emitting blue lightafter being excited by near ultraviolet light) is used as phosphorparticles in phosphor part 3B. Meanwhile, the same components as inEmbodiments B-20 and B-21 are designated by the same reference numeralsto omit redundant explanations.

Thus, in light emitting device 1B of the present embodiment, just as inEmbodiment B-25, since a phosphor powder that emits light after beingexcited by the light from luminous element 2 is dispersed in sealingpart 19, light output of a light synthesized from the light emitted fromluminous element 2, the light emitted from phosphor part 3B and thelight emitted from the phosphor powder is obtained. Consequently, justas in Embodiment B-25, by selecting material that emits near ultravioletlight as material of luminous layer part 21 in luminous element 2, bothphosphor part 3B and the phosphor powder in sealing part 19 will beexcited by the light emitted from luminous element 2 and emit lightsintrinsic to each of them. And a synthesized light can be obtained fromthose lights. In addition, the luminescent color of the phosphor powdercan be set identical to that of phosphor part 3B, differently from thecase in the present embodiment. With that configuration, it becomespossible to increase the light output and enhance the emissionefficiency because the light emitted from the phosphor powder issuperimposed on the light emitted from phosphor part 3B.

Embodiment B-41

Light emitting device 1B of the present embodiment has a basic structurethat is approximately the same as that in Embodiment B-2. As shown inFIG. 48, it is characterized in that a frame-shaped frame 18, encirclingluminous element 2 on one surface (upper surface in FIG. 48) ofinsulating substrate 16, is provided and sealing part 19 inside frame 18is formed of a phosphor part that is the same as that of phosphor part3B described in Embodiment B-2. The upper surface side of luminouselement 2 and sealing part 19 is cut off from oxygen or moisture contentof outside by a transparent lid 36 formed of glass, highly-hermeticresin or the like. Meanwhile, the same components as in embodiment B-2are designated by the same reference numerals to omit redundantexplanations. Lid 36 and sealing part 19 may be in direct contact witheach other or have a gap in between. However, when there is no gap, asemiconductor light-emitting device that is high in efficiency ofextracting light and brightness can be achieved. When they have a gap inbetween, it is preferable for the gap to be sealed with vacuum or inertgas.

Since sealing part 19 is formed of the phosphor part in the presentembodiment, it becomes possible to enhance sealing properties,transparency, light resistance and heat resistance of sealing part 19and to inhibit crack generations and peelings accompanying a long-termuse, by means of using the semiconductor light-emitting device member ofthe present invention as phosphor part, as described later.

In addition, in the present embodiment, lid 36 can inhibit an intrusionof external-factor such as moisture or oxygen, which acceleratesdeterioration of the phosphor and sealing resin, and volatilization ofgas generated by thermal or photolytic degradation of the sealing resin.This leads to another advantageous effect of reducing brightnessdecrease and peelings induced by shrinkage of the sealing part.

Meanwhile, the phosphor part 3B may be formed spherical with a diametera little larger than the visible wavelength and a large number of suchphosphor parts 3B may be dispersed in a solid medium that is made oflight-transmissible material, as shown in FIG. 49, unlike each of theabove embodiments, in which the phosphor part 3B is processed into arespective desired form or formed by means of sol-gel method. With thatconfiguration, the amount of the material used for the phosphor part canbe reduced while maintaining transparency of the phosphor part withrespect to the visible wavelength range, which can lead to costreduction.

Of course, a plurality of luminous elements 2 may constitute one unit ofmodule and a phosphor part may be disposed close to, at least a part of,the module as luminous material, unlike the above embodiments, in whicheach light-emitting device 1B has only one luminous element 2. In such acase, for example for a light-emitting device provided with a mold part11 in a shell-type shape, such as the one described in Embodiment B-1, aplurality of light-emitting devices may be mounted on the same printedboard so as to constitute one unit of module. As another example, for asurface-mount type light-emitting device, such as the one described inEmbodiment B-2, a plurality of luminous elements 2 may be mounted on thesame insulating substrate 16 so as to constitute one unit of module.

[Application of Semiconductor Light-Emitting Device Member]

The portion to which the semiconductor light-emitting device member ofthe present invention is applied in the light-emitting device(semiconductor light-emitting device) 1A, 1B, of each Embodiment of A-1,A-2, and B-1 to B-41 described above, is not particularly limited. Inthe above embodiments, the semiconductor light-emitting device member ofthe present invention is applied, as an example, as transparent member3A, or as phosphor parts 3B, 33, 34. However, as other examples, thesemiconductor light-emitting device member of the present invention canalso be suitably used as members that are constituting theabove-mentioned mold part 11, frame 18, sealing part 19 and the like. Byusing the semiconductor light-emitting device member of the presentinvention as these members, it becomes possible to obtain theabove-mentioned various advantageous effects such as superior sealingproperties, transparency, light resistance, heat resistance,film-formation capability and inhibition of crack generations andpeelings accompanying a long-term use.

When applying the semiconductor light-emitting device member of thepresent invention, it is preferable to make a modification thereto asappropriate, which is suitable for the portion to which the presentinvention is applied. For example, when the present invention is appliedto the phosphor part 3B, 33 or 34, the above-mentioned phosphorcomponents such as phosphor particles, phosphor ions and fluorescentdyes may be mixed into the semiconductor light-emitting device member ofthe present invention. Such a modification brings about an advantageouseffect of enhancing retention capacity of the phosphor, in addition tothe above-mentioned various advantageous effects.

Since the semiconductor light-emitting device member of the presentinvention is highly durable, it can seal a luminous element (such as anLED chip) as a sealing material (which is used as inorganic adhesive)superior in light resistance (UV resistance) and heat resistance, evenwhen it is used alone without including a phosphor.

If the above-mentioned inorganic particles are mixed into thesemiconductor light-emitting device member of the present invention, itbecomes possible to obtain the advantageous effects mentioned above inthe explanation for the combined use of inorganic particles, in additionto the above-mentioned various advantageous effects. Particularly, asemiconductor light-emitting device member of the present invention thatis adjusted to have a refractive index close to that of the luminouselement by the combined use of inorganic particles can act as a suitablelight extracting film.

[Uses or the Like of Semiconductor Light-Emitting Device]

The semiconductor light-emitting device can be used, for example, for alight-emitting device. In order to use the semiconductor light-emittingdevice for a light-emitting device, it is possible to place aphosphor-containing layer containing a mixture of red phosphor, bluephosphor and green phosphor, over a light source. In this case, it isnot always necessarily for the red, blue and green phosphors to be mixedin the same layer, but, for example, a layer containing the red phosphormay be stacked on the top of a layer containing the blue and greenphosphors.

In a light-emitting device, a phosphor-containing layer can be providedover the light source. The phosphor-containing layer can be provided asa contact layer located between the light source and the resinoussealing part, as a coating layer located outside the resinous sealingpart, or as a coating layer located inside an outside cap. Or otherwise,the resinous sealing may contain a phosphor.

As the resinous sealing part to be used, the semiconductorlight-emitting device member of the present invention can be used. Orotherwise, other kinds of resins can also be used. Such kinds of resinsusually include thermoplastic resin, thermosetting resin, light curingresin and the like. More specific examples include: methacrylic resinssuch as polymethacrylate methyl; styrene resins such as polystyrene andstyrene-acrylonitrile copolymer; polycarbonate resin; polyester resin;phenoxy resin; butyral resin; polyvinyl alcohol; cellulose resins suchas ethyl cellulose, cellulose acetate and cellulose acetate butyrate;epoxy resin; phenol resin; and silicone resin. Also, inorganic materialsof, for example, metal alkoxide and ceramic precursor polymer, asolution obtained by hydrolysis/polymerization of a solution containingmetal alkoxide by the sol gel method, or inorganic materials obtained bycuring a combination of such inorganic materials, such as inorganicmaterials containing siloxane bond, may be used. The resinous sealingsmay be used either as a single kind of them or as a mixture of two ormore kinds in any combination and in any ratio.

The amount of phosphor to be used, relative to that of the resinoussealing, is not particularly limited. However, it is usually 0.01 weightparts or more, preferably 0.1 weight parts or more, more preferably 1weight parts or more, and usually 100 weight parts or less, preferably80 weight parts or less, more preferably 60 weight parts or less, withrespect to 100 weight parts of the resinous sealing.

The resinous sealing may contain substances other than phosphors orinorganic particles. The examples of such substances include a dye usedfor correcting color tone, antioxidant, phosphorus compound stabilizerfor processing, oxidation and heat, light-resistant stabilizer such asUV absorbing agent and silane coupling agent. These substances can beused either as a single kind or as a mixture of two or more kinds in anycombination and in any ratio.

No particular limitation is imposed on the light source, but the onehaving peak wavelength in the range of 350 nm to 500 nm can bepreferably used. Concrete examples of the light source include alight-emitting diode (LED) and a laser diode (LD). Of these, a GaN LEDand a GaN LD, which utilize semiconductors based on GaN compound, arepreferable. This is because a GaN-based LED and a GaN-based LD havelight output and external quantum efficiency far greater than those ofan SiC-based LED and the like that emit the same range of light andtherefore they can give very bright luminescence with very low electricpower when used in combination with the above-mentioned phosphor. Forexample, when applying current load of 20 mA, a GaN-based LED andGaN-based LD usually have emission intensity 100 times or higher thanthat of an SiC-based ones. Among GaN LEDs and GaN LDs, the one having anAl_(X)Ga_(Y)N luminous layer, GaN luminous layer or In_(X)Ga_(Y)Nluminous layer is preferable. Among GaN LEDs in particular, the onehaving In_(X)Ga_(Y)N luminous layer is particularly preferable becauseemission intensity thereof is then very high. Among GaN LDs, the onehaving a multiple quantum well structure of In_(X)Ga_(Y)N layer and GaNlayer is particularly preferable because emission intensity thereof isthen very high.

In the above description, the X+Y usually takes a value in the range of0.8 to 1.2. A GaN-based LED having the above-mentioned kind of luminouslayer that is doped with Zn or Si or without any dopant is preferablefor the purpose of adjusting the luminescent characteristics.

GaN LED contains a such kind of luminous layer, p layer, n layer,electrode and substrate, as its basic components. Of these, the onehaving a heterostructure in which a luminous layer is sandwiched byn-type and p-type layers of Al_(X)Ga_(Y)N layer, GaN layer orIn_(X)Ga_(Y)N layer is preferable because it can have high emissionefficiency. Moreover, the one whose heterostructure is replaced by aquantum well structure is more preferable because it can have higheremission efficiency.

The light-emitting device emits white light. The emission efficiency ofthe light emitting device is 20 lm/W or more, preferably 22 lm/W ormore, more preferably 25 lm/W or more, and particularly preferably 28lm/W or more. The general color rendering index Ra thereof is 80 ormore, preferably 85 or more, and more preferably 88 or more.

The light-emitting device can be used, for example, as a lamp for alighting system, a back-lighting for a liquid crystal panel and thelike, various kinds of lighting systems such as ultra-thin-type lightingsystem, as well as an image display, by using it alone or a plurality ofthem in combination.

Furthermore, the semiconductor device member of the present inventioncan be suitably used for sealing an LED element, particularly blue orultraviolet LED element. Also, it can be preferably used for retaining aphosphor for a light source of a high-power lighting system, such as awhite LED or a warm-white LED, in which the light from an excitationlight source of blue or ultraviolet luminous element is converted in itswavelength by the phosphor. It can also be used as various displaymaterials shown below, for its excellent characteristics such as heatresistance, UV resistance and transparency.

The examples of the display materials include: peripheral materials of aliquid crystal display such as substrate material, optical guide plate,prism sheet, deflection plate (sic), phase difference plate, viewingangle-correction film, adhesive and polarizer-protective film of aliquid crystal display; sealant, antireflection film, optical correctionfilm, protective film for housing material or front glass, substitutionmaterial for front glass and adhesive of a color plasma display panel(PDP), which is one of next-generation flat-panel displays; substratematerial, optical guide plate, prism sheet, deflection plate (sic),phase difference plate, viewing angle-correction film, adhesive andpolarizer-protective film of a plasma address liquid crystal (PALC)display; protective film for front glass, substitution material forfront glass and adhesive of an organic EL (electroluminescence) display;and various film substrates, protective film for front glass,substitution material for front glass and adhesive of a field emissiondisplay (FED).

The semiconductor device member of the present invention is superior inadhesion and it can be laminated by means of recoating, which has beendifficult for conventionally-known addition condensation type siliconeresins. Making the most of this characteristic, a laminar structurehaving different refractive indexes can be formed by such a method that,for example, a low-refractive-index layer of the semiconductor devicemember of the present invention that consists mainly of methyl group islaminated with a high-refractive-index layer that is introduced withzirconia nano particles or high-refractive-index organic groups such asphenyl group. This can form a light guiding layer that is highly durableand excellent in adhesion and flexibility easily.

EXAMPLE

The present invention will be described more specifically below by usingsome examples, but these examples are for explaining the presentinvention and do not intend to limit the present invention to theseaspects.

[I] First Example Group [I-1] Analysis Method

Analyses were performed according to the following procedures for thesemiconductor device member of each Example and Comparative Exampledescribed later.

[I-1-1] Measurement of Weight Loss at the Time of Heating (TG-DTA)

The weight loss at the time of heating was measured by athermogravimetric/differential thermal analysis (hereinafter abbreviatedas “TG-DTA” as appropriate) apparatus (TG/DTA6200, manufactured by SeikoInstrument Inc.) for a 10-mg fragment of the semiconductor device memberof each Example and Comparative Example so that it was heated from 35°C. to 500° C. at a temperature rising rate of 10° C./min under200-ml/min flow of air. A fragment of which precise weighing wasdifficult was treated in such a manner that, for example, a fragmentwithin the range of 10±1 mg was taken as a fragment of 10 mg, inconsideration of the significant figure range.

[I-1-2] Adhesion Evaluation Method

(1) A hydrolyzed/polycondensated liquid (semiconductor-device-memberformation liquid) of pre-curing semiconductor device member of eachExample and Comparative Example was dropped into a silver-plated coppercup with a diameter of 9 mm and a depth at the recess of 1 mm and thencured under a predetermined curing conditions, thereby preparing asample for measurement (semiconductor device member).(2) The obtained samples for measurement were placed on an aluminumplate, which was coated with a thin layer of silicone grease fordissipating heat, with 1 mm in thickness, 25 mm in length and 70 mm inwidth, and let absorb moisture in an atmosphere of 85-° C. temperatureand 85-% humidity (hereinafter referred to as “moisture absorptionenvironment” as appropriate) for 20 hours.(3) The samples for measurement, which absorbed moisture, were taken outfrom the moisture absorption environment of the above-mentioned (2) andthen cooled to room temperature (20° C. to 25° C.). The samples formeasurement, which absorbed moisture and were cooled to roomtemperature, were put on a hot plate, whose temperature was set at 260°C., together with the aluminum plate and kept for 1 minute. Under thiscondition, the temperature of the samples for measurement itself reached260° C. in 50 seconds, and then they were kept at 260° C. for 10seconds.(4) The post-heated samples were then put on a cooling plate, which wasmade of stainless steel and set at room temperature, together with thealuminum plate so as to cool them to room temperature. Then theexistence or the nonexistence of a peeling of the samples formeasurement from the above-mentioned copper cup was observed both byvisual inspection and with a microscope. Even a sample which wasobserved to have just a small peeling was labeled as “peelinggenerated”.(5) The ratio of peeling of the above-mentioned samples for measurementwas determined by conducting the above operations (2), (3) and (4) foreach of 10 samples for measurement.

[I-1-3] Hardness Measurement

Hardness (Shore A) of the semiconductor device member of each Exampleand Comparative Example was measured based on JIS K6253 using an A-type(durometer type A) rubber hardness scale manufactured by Kori Seiki MFG.Co., Ltd.

[I-1-4] Heat Resistance Test

A sample of 5 cm in diameter and 1.0 mm in film thickness of thesemiconductor device member of each Example and Comparative Example,which was formed with a Teflon (registered trademark) petri dish, waskept in a forced-air drier at temperature of 200° C. for 500 hours. Thechange in transmittance of this sample with respect to light of 400-nmwavelength before and after the test was analyzed.

[I-1-5] Measurement of Silicon Content

A singly cured product of the semiconductor device member of eachExample and Comparative Example was ground to pieces of about 100 μm andkept in a platinum crucible to be fired in the air at 450° C. for 1hour, then at 750° C. for 1 hour and then at 950° C. for 1.5 hours.After removal of carbon components, the small amount of residue obtainedis added with a 10-fold amount or more of sodium carbonate and thenheated by a burner to melt it. Then the melted product was cooled andadded with desalted water, being diluted to several ppm in silicon whileadjusting pH value to around neutrality using hydrochloric acid. Thenthe ICP spectrometry was performed using “SPS1700HVR” manufactured bySeiko Instruments Inc.

[I-1-6] Continuous Lighting Test

A semiconductor light-emitting device was prepared using the sealantliquid obtained in each Example and Comparative Example. A drivingcurrent of 20 mA was passed through each semiconductor light-emittingdevice to continuously light at temperature of 85° C. and relativehumidity of 85%. The brightness after elapse of 500 hours was comparedwith that before the lighting test.

In the above test, each semiconductor light-emitting device was preparedby the following procedure. Namely, a surface-mount type LED element 103comprised of a cup 101 and an LED chip 102 was first prepared as LEDlight source, as shown in FIG. 50. The cup 101 was formed ofpolyphthalamide, and an electrode (not shown in the drawings) wasprovided on the bottom thereof. As LED chip 102, one having a face-uptype GaN semiconductor of 405-nm emission-peak wavelength as itsluminous layer was used. The LED chip 102 was attached by die bonding onthe surface of the electrode that was provided inside the cup 101, usinga die bonding device (“Manual Die Bonder” manufactured by Westbond) andepoxy resin as die bonding agent. Another electrode (not shown in thedrawings) was provided on the top of LED chip 102. This electrode waselectrically connected to the electrode of the cup 101 by wire bondingusing a wire bonder “MB-2200” manufactured by Nippon Avionics Co., Ltd.with gold wire. The sealant liquid, prepared in each Example andComparative Example, was dropped using a micro pipet in the cup 101until the height thereof reached the upper edge of the cup. Then thesealant liquid was cured under a predetermined temperature condition,thereby obtaining a semiconductor light-emitting device comprising atransparent sealing layer (semiconductor device member).

[I-1-7] Heat Cycle Test

The sealant liquid of each Example and Comparative Example was pottedinto a surface-mount cup (an empty cup without a chip) made ofpolyphthalamide, and it was cured under predetermined curing conditions.This applied product in the empty PKG was placed in a small-sizeenvironment tester, “SH-241”, manufactured by ESPEC CORP., and a heatcycle test of 200 cycles was carried out without a humidity regulation.The one cycle includes letting the product stand at −40° C. for 30minutes, rising the temperature from −40° C. to 100° C. over 1 hour,letting the product stand at 100° C. for 30 minutes, and falling thetemperature from 100° C. to −40° C. over 1 hour. This one cycle took 3hours in total. The sample was taken out after the 200 cycles, and theexistence or nonexistence of a peeling at the contact portion betweenthe cup and the sealant liquid was observed using a stereoscopicmicroscope.

[I-2] Experimental Operations Example I-1

140 g of double-ended silanol dimethyl silicone oil (XC96-723,manufactured by GE Toshiba Silicones Co., Ltd.), 14 g ofphenyltrimethoxysilane, and 0.308 g of zirconium tetraacetylacetonatepowder as a catalyst, were weighed into a three-necked flask fitted witha stir wing and a condenser, and the mixture was stirred for 15 minutesat room temperature until the catalyst dissolved sufficiently.Thereafter, the reaction solution was heated until the temperaturereached 120° C. and kept at this temperature under total reflux for 30minutes while being stirred, for initial hydrolysis.

Then, nitrogen gas was blown in by means of SV20, and methanol formed,water and low-boiling silicon components produced as by-product weredistilled off, while stirring was continued at 120° C., to conductpolymerization reaction further for 6 hours. In this context, “SV” is anabbreviation of “Space Velocity” and indicates a blowing-in volume perunit time. Therefore, “SV 20” means that N₂ with volume of 20 timeslarger than that of the reaction solution was bubbled in per 1 hour.

Nitrogen gas blowing-in was stopped and the reaction solution wastransferred to a round-bottomed flask after cooled to room temperature.Then the methanol, water and low-boiling silicon components, eachremaining in just a little amount, were distilled off in an oil bathusing a rotary evaporator at 120° C. at 1 kPa for 20 minutes. Thereby, asealant liquid (semiconductor-device-member formation liquid) withoutcontaining a solvent was prepared.

2 g of the above-mentioned sealant liquid was placed in a Teflon(registered trademark) petri dish with a diameter of 5 cm, and the petridish was held in an explosion-proof furnace under a mild stream of airat 110° C. for 1 hour and then 150° C. for 3 hours. Thereby, anindependent, circular, and elastomer-like film with thickness of about 1mm was obtained. Using this as a sample, the above-mentioned [I-1-1]measurement of weight loss at the time of heating (TG-DTA), [I-1-3]hardness measurement, [I-1-4] heat resistance test, and [I-1-5]measurement of silicon content were performed. The results are shown inTable 2. In Table 2, numerical values in the row of TG-DTA are negativenumbers, which means that the weights were reduced.

In addition, using the sealant liquid, tests of the above-mentioned[I-1-2] adhesion evaluation method, [I-1-6] continuous lighting test,and [I-1-7] heat cycle test were performed. In these tests, the sealantliquid was cured being kept at 90° C. for 2 hours, at 110° C. for 1hour, and then at 150° C. for 3 hours. This corresponds to theabove-mentioned “predetermined curing conditions” in each explanationfor the tests. The results are shown in Table 2.

Example I-2

100 g of double-ended silanol dimethyl silicone oil (XC96-723,manufactured by GE Toshiba Silicones Co., Ltd.), 10 g ofphenyltrimethoxysilane, and 22 g of zirconium tetra n-propoxide solution(in which 5 weight parts of 75-weight % n-propanol solution of zirconiumtetra n-propoxide was diluted with 95 weight parts of toluene) ascatalyst were weighed into a three-necked flask fitted with a stir wingand a condenser. The mixture was stirred at room temperature underatmospheric pressure for 15 minutes to perform initial hydrolysis, andthen heated under stirring at about 50° C. for 8 hours. Then thereaction solution was allowed to cool to room temperature, andtransferred to a round-bottomed flask so as to distill off the solvent,and alcohol, water and low-boiling silicon components that were producedduring the reaction, using a rotary evaporator at 50° C. and 1 kPa for30 minutes. Thereby, a sealant liquid without solvent was obtained.

2 g of the above-mentioned sealant liquid was placed in a Teflon(registered trademark) petri dish with a diameter of 5 cm, in the sameway as Example I-1. Then the petri dish was held in an explosion-prooffurnace under a mild stream of air at 110° C. for 1 hour, and then 150°C. for 3 hours. Thereby, an independent, circular, and elastomer-likefilm with thickness of about 1 mm was obtained. Using this as a sample,the above-mentioned [I-1-1] measurement of weight loss at the time ofheating (TG-DTA), [I-1-3] hardness measurement, [I-1-4] heat resistancetest, and [I-1-5] measurement of silicon content were performed. Theresults are shown in Table 2.

In addition, using the sealant liquid, tests of the above-mentioned[I-1-2] adhesion evaluation method, [I-1-6] continuous lighting test,and [I-1-7] heat cycle test were performed. In these tests, the sealantliquid was cured under the same conditions as Example I-1. Thiscorresponds to the above-mentioned “predetermined curing conditions” ineach explanation for the tests. The results are shown in Table 2.

Example I-3

27 g of methylhydrogen polysiloxane (KF-99, manufactured by Shin-EtsuChemical Co., Ltd.), 32.41 g of vinyltrimethoxysilane manufactured byTokyo Chemical Industry Co., Ltd., and an addition condensationcatalyst, 5 ppm in terms of platinum element, were weighed into a 100-ccflask fitted with a stir wing and a Dimroth condenser, and they weremixed homogenously while being stirred. The liquid was heated at 100° C.for 20 hours under nitrogen atmosphere, thereby preparing a methoxygroup-containing polydimethylsiloxane with a viscosity of 300 mPa·s. Themeasurement of the amount of residual vinyl group in the liquid by meansof ¹H-NMR found that it disappeared completely. To 1 g of the liquid, 10g of double-ended silanol polydimethylsiloxane (XC96-723, manufacturedby Momentive Performance Materials Inc.) and 0.011 g of zirconiumtetraacetylacetonate powder as condensation catalyst were added, in a100-ml round-bottomed flask. After a tight closure, the mixture wasstirred at room temperature until the catalyst completely dissolved.Subsequently, the reaction solution was heated up to 110° C. undernitrogen atmosphere with a Dimroth condenser fitted, and then it wasrefluxed for 30 minutes. After cooling the reaction solution down toroom temperature, the round-bottomed flask was connected to a rotaryevaporator, and then the methanol, water and low-boiling siliconcomponents, each remaining in just a little amount, were distilled offin an oil bath at 120° C. and 1 kPa for 30 minutes. Thereby, a sealantliquid (semiconductor-device-member formation liquid) without containinga solvent was prepared.

2 g of the above-mentioned sealant liquid was placed in a Teflon(registered trademark) petri dish with a diameter of 5 cm, and the petridish was held in an explosion-proof furnace under a mild stream of airat 110° C. for 1 hour and then 150° C. for 3 hours. Thereby, anindependent, circular, and elastomer-like film with thickness of about 1mm was obtained. Using this as a sample, the above-mentioned [I-1-1]measurement of weight loss at the time of heating (TG-DTA), [I-1-3]hardness measurement, [I-1-4] heat resistance test, and [I-1-5]measurement of silicon content were performed. The results are shown inTable 2.

In addition, using the sealant liquid, tests of the above-mentioned[I-1-2] adhesion evaluation method, [I-1-6] continuous lighting test,and [I-1-7] heat cycle test were performed. In these tests, the sealantliquid was cured being kept at 90° C. for 2 hours, at 110° C. for 1hour, and then at 150° C. for 3 hours. This corresponds to theabove-mentioned “predetermined curing conditions” in each explanationfor the tests. The results are shown in Table 2.

Comparative Example I-1

100 g of double-ended silanol dimethyl silicone oil (XC96-723,manufactured by GE Toshiba Silicones Co., Ltd.), 10 g ofphenyltrimethoxysilane, and 22 g of aluminum triacetylacetonate methanolsolution of 5 weight % as a catalyst were weighed into a three-neckedflask fitted with a stir wing and a condenser, and the mixture wasstirred at room temperature under atmospheric pressure for 15 minutes.After initial hydrolysis was performed, the mixture was caused to refluxwhile being stirred at about 75° C. for 4 hours. Subsequently, methanoland low-boiling silicon components were distilled off at a normalpressure until the internal temperature reached 100° C., and then themixture was further caused to reflux while being stirred at 100° C. for4 hours. The reaction mixture was cooled down to the room temperature toprepare a sealant liquid without containing a solvent.

2.5 g of the above-mentioned sealant liquid was placed in a Teflon(registered trademark) petri dish with a diameter of 5 cm, and the petridish was held in an explosion-proof furnace under a mild stream of airat 50° C. for 30 minutes, then 110° C. for 1 hour, and then 150° C. for3 hours. Thereby, an independent, circular, and elastomer-like film withthickness of about 1 mm was obtained. Using this as a sample, theabove-mentioned [I-1-1] measurement of weight loss at the time ofheating (TG-DTA), [I-1-3] hardness measurement, [I-1-4] heat resistancetest, and [I-1-5] measurement of silicon content were performed. Theresults are shown in Table 2.

In addition, using the sealant liquid, tests of the above-mentioned[I-1-2] adhesion evaluation method, [I-1-6] continuous lighting test,and [I-1-7] heat cycle test were performed. In these tests, the sealantliquid was cured being kept at 50° C. for 30 minutes, then at 120° C.for 1 hour, and then at 150° C. for 3 hours. This corresponds to theabove-mentioned “predetermined curing conditions” in each explanationfor the tests. The results are shown in Table 2.

Comparative Example I-2

A commercially available silicone resin (JCR6101UP, manufactured by DowCorning Toray Company, Limited) which is used as a molding agent for asemiconductor light-emitting device was on hand as the sealant liquid.

30 g of the sealant liquid was applied onto a Teflon (registeredtrademark) plate using an applicator, and, after vacuum deaeration at25° C. for 1 hour, was dried by heating at 150° C. for 2 hours. Anelastomer-like film with the thickness of about 1 mm was obtained bypeeling off the applied product from the plate. Using this as a sample,the above-mentioned [I-1-1] measurement of weight loss at the time ofheating (TG-DTA), [I-1-3] hardness measurement, [I-1-4] heat resistancetest, and [I-1-5] measurement of silicon content were performed. Theresults are shown in Table 2.

In addition, using the sealant liquid, tests of the above-mentioned[I-1-2] adhesion evaluation method, [I-1-6] continuous lighting test,and [I-1-7] heat cycle test were performed. In these tests, the sealantliquid was cured being kept at 150° C. for 2 hours. This corresponds tothe above-mentioned “predetermined curing conditions” in eachexplanation for the tests. The results are shown in Table 2.Incidentally, the sealing member obtained under the above-mentionedpredetermined curing conditions was a sealing member in an elastomerstate.

Comparative Example I-3

A commercially available two-component silicone resin (XJL0012,manufactured by PELNOX, LTD.) which is used as a molding agent for asemiconductor light-emitting device was prepared as the sealant liquid.

2 g of the above-mentioned sealant liquid was placed in a Teflon(registered trademark) petri dish with a diameter of 5 cm, and the petridish was held in an explosion-proof furnace under a mild stream of airat 150° C. for 3 hours. Thereby, an independent, circular, transparent,and hard film with thickness of about 1 mm was obtained. Using this as asample, the above-mentioned [I-1-1] measurement of weight loss at thetime of heating (TG-DTA), [I-1-3] hardness measurement, [I-1-4] heatresistance test, and [I-1-5] measurement of silicon content wereperformed. The results are shown in Table 2.

In addition, using the sealant liquid, tests of the above-mentioned[I-1-2] adhesion evaluation method, [I-1-6] continuous lighting test,and [I-1-7] heat cycle test were performed. In these tests, the sealantliquid was cured being kept at 150° C. for 3 hours. This corresponds tothe above-mentioned “predetermined curing conditions” in eachexplanation for the tests. The results are shown in Table 2.Incidentally, the sealing member obtained under the above-mentionedpredetermined curing conditions was a transparent and hard sealingmember.

Comparative Example I-4

30.80 g of methyl silicate (MKC silicate MS51, manufactured byMitsubishi Chemical Corporation), 56.53 g of methanol, 6.51 g of water,and 6.16 g of a catalyst of 5-% methanol solution of acetylacetonealuminum salt were transferred to a vessel that can be closed tightlyand then mixed. After tight closure, the mixture was heated in a hotwater bath at 50° C. for 8 hours under stirring with a stirrer and thenreturned to room temperature. A hydrolyzed/polycondensated liquid wasthus prepared.

10 ml of the above-mentioned hydrolyzed/polycondensated liquid wasplaced in a Teflon (registered trademark) petri dish with a diameter of5 cm, and dried under the same conditions as in Example I-1. Thereby, aglass film of about 0.3 mm in thickness was obtained. However, in thecourse of drying, a large amount of cracks were generated and the glassfilm broke into pieces. Therefore, a circular, transparent glass filmcould not be isolated. However, by using this, [I-1-5] measurement ofsilicon content was performed.

On the other hand, the hydrolyzed/polycondensated liquid was droppedonto a GaN-based semiconductor light-emitting device having a luminouswavelength of 405 nm using a micro pipet. The device was kept at 35° C.for 30 minutes, and subsequently at 50° C. for 1 hour, to perform thefirst drying, and then kept at 150° C. for 3 hours to perform the seconddrying. However, a large amount of cracks appeared and therefore thefilm could not be used as a sealing member (semiconductor devicemember).

TABLE 2 Comparative Comparative Comparative Comparative Example I-1Example I-2 Example I-3 Example I-1 Example I-2 Example I-3 Example I-4TG-DTA [weight %] −32 −28 −46 −81 −53 −16 −2 Adhesion [%] 0 0 0 0 40 100(*) Hardness (Shore A) 33 15 20 27 37 90< (*) Heat resistance 100 97 97103 104 7 (*) [%] Silicon content 38 38 38 38 35 21 43 [weight %]Continuous no unlit, no no unlit, no no unlit, no no unlit, no nodecrease decrease in (*) lighting test peelings, no peelings, nopeelings, no peelings, no in brightness decrease in decrease in decreasein decrease in brightness, during the brightness brightness brightnessbrightness unlit ratio: test, unlit 67% ratio: 100% Heat cycle test 0 010 75 10 50 (*) (ratio of peeling) [%] *Not measurable because crackswere generated

[I-3] Summary

It is evident from the above-mentioned Examples that the semiconductordevice member of the present invention excels in heat resistance,adhesion to semiconductor device surfaces including silver surfaces,which are used often for electrodes and reflectors, and light resistance(especially, UV resistance). This leads to the exhibition of its abilityto maintain its performances stably in the continuous lighting testunder an accelerated environment of high temperature and high humidity,without causing a peeling, unlit device or brightness decrease due toadhesion decrease or degradation. Furthermore, the semiconductor devicemember of the present invention is highly resistant to thermal shock andshows no peelings in the heat cycle test, since it is high in adhesionto semiconductor devices and excels in its plasticity. Therefore, asemiconductor device having a superior reliability can be provided.

In contrast, the semiconductor device member of Comparative Example I-1shows no coloring in the heat resistance test, in the same way as themember of each Example, but is insufficient in adhesion, leading to theoccurrence of peeling in the heat cycle test. The semiconductor devicemember of Comparative Example I-2 shows no coloring in the heatresistance test, but is insufficient in adhesion to the silver surfacein comparison with Examples I-1 and I-2 and Comparative Example I-1,leading to the occurrence of peeling and unlit device even in thecontinuous lighting test, as well as in the heat cycle test. Thesemiconductor light-emitting device member of Comparative Example I-3 issmall in weight loss at the time of heating, since it is rigid and highin its degree of crosslinking due to a large amount of trifunctionalsilicons contained therein. However, since it is low in adhesion andpoor in plasticity, all the devices were unlit in the continuouslighting test and the ratio of peeling was high in the heat cycle test.In addition, it shows considerable coloring, which originates fromadditives such as adhesion improvement agent, in the heat resistancetest and also degradation in brightness in the continuous lighting test.The member obtained in Comparative Example I-4 is normally expected tobe the highest in heat resistance and light resistance, since itconsists of SiO₂. However, it could not be formed into a thick film oftransparent sealing body, because the internal stress thereof during thecuring originating from the shrinkage caused by desolvation ordehydration condensation is large and thus cracks are liable to appearduring the curing.

The following forced peeling test showed that use of the semiconductordevice member of the present invention together with a surface that issurface-treated for adhesion improvement can achieve an advantageouseffect of further improvement in adhesion.

[Forced Peeling Test]

Example I-3 (sic): In a glass beaker, γ-methacryloxypropyltrimethoxysilane was added to 1-% acetic acid aqueous solution sothat the concentration was 1 weight %, thereby preparing 100 g of aprocessing liquid. The liquid was stirred using a magnetic stirrer atroom temperature for 1 hour, thereby preparing a transparent hydrolyzingliquid. A borosilicate glass plate was immersed in the hydrolyzingliquid and subjected to a surface treatment using a hot water bath at50° C. for 1 hour. The post-treated glass plate was taken out from theprocessing liquid and washed lightly with water, avoiding contact ofhands with the treated surfaces, followed by draining. Subsequently, itwas baked with a forced-air drier of 100° C. for 1 hour. Then, 0.5 ml ofthe semiconductor-device-member formation liquid of Example I-1 wasdropped on the surface of an untreated glass plate and thesurface-treated glass plate, respectively. Then they were heated at 150°C. for 1.5 hours to be cured, thereby forming films with thicknesses of50 μm. The films were then tried to be peeled by holding one edgethereof and drawing it slowly using tweezers. The film applied on theglass plate that had no surface treatment was peeled, with a certainamount of residues remained on the interface between the film and theglass. On the other hand, the film applied on the surface-treated glassplate was not able to be peeled, but it was broken.

As a result, the semiconductor device member of the present invention issuperior in balance among heat resistance, light resistance, adhesionand film-formation capability, and it exhibits higher reliability thanconventional semiconductor device members even under severe serviceconditions. In particular, since it is superior in transparency and UVresistance, it can be used preferably as a semiconductor light-emittingdevice member.

[II] Second Example Group [II-1] Analysis Method

Analyses were performed according to the following procedures for thesemiconductor device member of each Example and Comparative Exampledescribed later.

[II-1-1] Heat Resistance Test

A sample of 5 cm in diameter and 1.0 mm in film thickness of the sealant(semiconductor device member) of each Example and Comparative Example,which was formed with a Teflon (registered trademark) petri dish, waskept in a forced-air drier at temperature of 200° C. for 500 hours. Thechange in transmittance of this sample with respect to light of 400-nmwavelength before and after the test was analyzed.

[II-1-2] UV Resistance Test

A sample of 5 cm in diameter and 0.5 mm in film thickness of the sealant(semiconductor device member) of each Example and Comparative Example,which was formed with a Teflon (registered trademark) petri dish, wasirradiated with an ultraviolet light. The maintenance rate oftransmittance of the film with respect to light of 400-nm wavelengthbefore and after the irradiation was measured.

Irradiation equipment: Accelerated light resistance test apparatus,Metering Weather Meter MV30, manufactured by Suga Test Instruments Co.,Ltd.

Irradiation wavelength: Wavelength of 370 nm or longer, and centerwavelength of 380 nm. This was created by filtering an irradiation lighthaving wavelength of 255 nm or longer and main wavelengths of 300 nm to450 nm (with emission lines from 480 nm to 580 nm) using a UV protectionfilm.

Irradiation time: 72 hours

Radiant intensity: 0.6 kW/m²

[II-1-3] Continuous Lighting Test

A semiconductor light-emitting device was prepared using the sealantliquid obtained in each Example and Comparative Example to be describedlater. For each of the semiconductor light-emitting devices, thefollowing continuous lighting test was performed.

[II-1-3-1] Preparation of Semiconductor Light-Emitting Device

After a square chip measuring 900 μm per side (C460-XB900, manufacturedby Cree Inc.) was fixed to a sub mount with Au—Sn eutectic solder, thesub mount was fixed to a metal package, manufactured by MCO Co., ltd.,with Au—Sn eutectic solder. The electrode on the chip and the pin on themetal package were connected by means of wire bonding using a gold wire.

[II-1-3-2] Continuous Lighting Test

The chip (semiconductor element) was illuminated at 85-° C. temperatureand 85-% relative humidity for 500 hours in a continuous manner with 350mA of driving current while maintaining the temperature of the emissionsurface at 100±10° C. The percentage of brightness after 500 hoursillumination relative to that of just after switched on (brightnessretention rate) was measured.

The brightness measurement was carried out in a thermostat bath of 25°C. using a spectroscope, “USB2000”, manufactured by Ocean Optics, Inc.(wavelength range: 380 nm to 800 nm, light-reception method: integratingsphere of 100 mmφ). Heat was dissipated with an aluminum plate withthickness of 3 mm via a heat-conductive insulation heat, in order toprevent temperature rising.

[II-1-4] Adhesion Evaluation Method

(1) A hydrolyzed/polycondensated liquid (semiconductor-device-memberformation liquid) of pre-curing sealant of each Example and ComparativeExample was dropped into a silver-plated copper cup with a diameter of 9mm and a depth at the recess of 1 mm and then cured under apredetermined curing conditions, thereby preparing a sample formeasurement.(2) The obtained samples for measurement were placed on an aluminumplate, which was coated with a thin layer of silicone grease fordissipating heat, with 1 mm in thickness, 25 mm in length and 70 mm inwidth, and let absorb moisture in an atmosphere of 85-° C. temperatureand 85-% humidity (hereinafter referred to as “moisture absorptionenvironment” as appropriate) for 1 hour.(3) The samples for measurement, which absorbed moisture, were taken outfrom the moisture absorption environment of the above-mentioned (2) andthen cooled to room temperature (20° C. to 25° C.). The samples formeasurement, which absorbed moisture and were cooled to roomtemperature, were put on a hot plate, whose temperature was set at 260°C., together with the aluminum plate and kept for 1 minute. Under thiscondition, the temperature of the samples for measurement itself reached260° C. in 50 seconds, and then they were kept at 260° C. for 10seconds.(4) The post-heated samples were then put on a cooling plate, which wasmade of stainless steel and set at room temperature, together with thealuminum plate so as to cool them to room temperature. Then theexistence or the nonexistence of a peeling of the samples formeasurement from the above-mentioned copper cup was observed both byvisual inspection and with a microscope. Even a sample which wasobserved to have just a small peeling was labeled as “peelinggenerated”.(5) The ratio of peeling of the above-mentioned samples for measurementwas determined by conducting the above operations (2), (3) and (4) foreach of 10 samples for measurement.

[II-2] Experimental Operations Example II-1

140 g of double-ended silanol dimethyl silicone oil (XC96-723,manufactured by GE Toshiba Silicones Co., Ltd.), 14 g ofphenyltrimethoxysilane, and 0.308 g of zirconium tetraacetylacetonatepowder as a catalyst, were weighed into a three-necked flask fitted witha stir wing and a condenser, and the mixture was stirred for 15 minutesat room temperature until the catalyst dissolved sufficiently.Thereafter, the reaction solution was heated until the temperaturereached 120° C. and kept at this temperature under total reflux for 30minutes while being stirred, for initial hydrolysis.

Then, nitrogen gas was blown in by means of SV20, and methanol formed,water and low-boiling silicon components produced as by-product weredistilled off, while stirring was continued at 120° C., to conductpolymerization reaction further for 6 hours. In this context, “SV” is anabbreviation of “Space Velocity” and indicates a blowing-in volume perunit time. Therefore, “SV 20” means that N₂ with volume of 20 timeslarger than that of the reaction solution was blowed in per 1 hour.

Nitrogen gas blowing-in was stopped and the reaction solution wastransferred to a round-bottomed flask after cooled to room temperature.Then the methanol, water and low-boiling silicon components, eachremaining in just a little amount, were distilled off in an oil bathusing a rotary evaporator at 120° C. at 1 kPa for 20 minutes. Thereby, asealant liquid (semiconductor-device-member formation liquid) withoutcontaining a solvent was prepared.

2 g of the above-mentioned sealant liquid was placed in a Teflon(registered trademark) petri dish with a diameter of 5 cm, and the petridish was held in an explosion-proof furnace under a mild stream of airat 110° C. for 1 hour and then 150° C. for 3 hours. Thereby, anindependent, circular, and elastomer-like film with thickness of about 1mm was obtained. Using this as a sample, each evaluation of theabove-mentioned [II-1] was performed. The results are shown in Table 3.

Example II-2

100 g of double-ended silanol dimethyl silicone oil (XC96-723,manufactured by GE Toshiba Silicones Co., Ltd.), 10 g ofphenyltrimethoxysilane, and 22 g of zirconium tetra n-propoxide solution(in which 5 weight parts of 75-weight % n-propanol solution of zirconiumtetra n-propoxide was diluted with 95 weight parts of toluene) ascatalyst were weighed into a three-necked flask fitted with a stir wingand a condenser. The mixture was stirred at room temperature underatmospheric pressure for 15 minutes to perform initial hydrolysis, andthen heated under stirring at about 50° C. for 8 hours. Then thereaction solution was allowed to cool to room temperature, andtransferred to a round-bottomed flask so as to distill off the solvent,and alcohol, water and low-boiling silicon components that were producedduring the reaction, using a rotary evaporator at 50° C. and 1 kPa for30 minutes. Thereby, a sealant liquid without solvent was obtained.

2 g of the above-mentioned sealant liquid was placed in a Teflon(registered trademark) petri dish with a diameter of 5 cm, in the sameway as Example II-1. Then the petri dish was held in an explosion-prooffurnace under a mild stream of air at 110° C. for 1 hour, and then 150°C. for 3 hours. Thereby, an independent, circular, and elastomer-likefilm with thickness of about 1 mm was obtained. Using this as a sample,each evaluation of the above-mentioned [II-1] was performed. The resultsare shown in Table 3.

Example II-3

27 g of methylhydrogen polysiloxane (KF-99, manufactured by Shin-EtsuChemical Co., Ltd.), 32.41 g of vinyltrimethoxysilane manufactured byTokyo Chemical Industry Co., Ltd., and an addition condensationcatalyst, 5 ppm in terms of platinum element, were weighed into a 100-ccflask fitted with a stir wing and a Dimroth condenser, and they weremixed homogenously while being stirred. The liquid was heated at 100° C.for 20 hours under nitrogen atmosphere, thereby preparing a methoxygroup-containing polydimethylsiloxane with a viscosity of 300 mPa·s. Themeasurement of the amount of residual vinyl group in the liquid by meansof ¹H-NMR found that it disappeared completely. To 1 g of the liquid, 10g of double-ended silanol polydimethylsiloxane (XC96-723, manufacturedby Momentive Performance Materials Inc.) and 0.011 g of zirconiumtetraacetylacetonate powder as condensation catalyst were added, in a100-ml round-bottomed flask. After a tight closure, the mixture wasstirred at room temperature until the catalyst completely dissolved.Subsequently, the reaction solution was heated up to 110° C. undernitrogen atmosphere with a Dimroth condenser fitted, and then it wasrefluxed for 30 minutes. After cooling the reaction solution down toroom temperature, the round-bottomed flask was connected to a rotaryevaporator, and then the methanol, water and low-boiling siliconcomponents, each remaining in just a little amount, were distilled offin an oil bath at 120° C. and 1 kPa for 30 minutes. Thereby, a sealantliquid (semiconductor-device-member formation liquid) without containinga solvent was prepared.

Using the sealant liquid, tests of the above-mentioned [II-1-1] heatresistance test, [II-1-2] UV resistance test, [II-1-3] continuouslighting test, and [II-1-4] adhesion evaluation method were performed.In these tests, the sealant liquid was cured being kept at 90° C. for 2hours, then at 110° C. for 1 hour, and then at 150° C. for 3 hours. Thiscorresponds to the above-mentioned “predetermined curing conditions” ineach explanation for the tests. The results are shown in Table 3.

Comparative Example II-1 to Comparative Example II-4

By using commercially available sealants shown in Table 3, eachevaluation of the above-mentioned [II-1] was performed. The results areshown in Table 3.

TABLE 3 Example Example Example Comparative Comparative ComparativeComparative II-1 II-2 II-3 Example II-1 Example II-2 Example II-3Example II-4 Company name of the Dow Corning Dow Corning GE Toshiba GEToshiba product Toray Toray Product name EG6301 JCR6175 IVS4012 IVS5332Functional group Methoxy Methoxy Methoxy Unknown Methoxy Ethoxy groupEthoxy group capable of forming a group, group, group, group, Epoxyhydrogen bond Silanol Silanol Silanol group group group groupTransmittance 100 98 97 95 88 Unmeasureable 60 retention rate (%)because [II-1-1] Heat unable to resistance test prepare disc due to gelstate Transmittance 80≦ 80≦ 80≦ 80≦ 80≦ 80≦ 80≦ retention rate (%) in[II-1-2] UV resistance test Brightness retention 98 100 95 89 43 (−)52.1 rate (%) in [II-1-3] Continuous lighting test ratio of alumina 0 00 0 90 100 0 peeling in ceramic [II-1-4] package Adhesion Silver- 0 0 070 80 100 50 evaluation plated (%) metal package Observation No No NoYellow Yellow Numerous Numerous change change change coloration ofcoloration of foamings foamings alumina alumina generated generatedpackage just package just by moisture by moisture absorption absorption,Fuming during reflow

INDUSTRIAL APPLICABILITY

The semiconductor device member of the present invention is notparticularly limited in its use and can be used for various purposestypified by a member for sealing (namely, a sealant for) a semiconductorelement or the like. Among them, it can be particularly preferably usedas a sealant or a light extracting film for a blue LED or anear-ultraviolet LED, or as a phosphor-retaining agent for a high-powerwhite LED, in which a luminous element such as a blue LED, anear-ultraviolet LED or the like is used as its light source.

Furthermore, the semiconductor device member of the present inventioncan be suitably used for sealing an LED element, particularly blue orultraviolet LED element. Also, it can be preferably used for retaining aphosphor for a light source of a high-power lighting system, such as awhite LED or a warm-white LED, in which the light from an excitationlight source of blue or ultraviolet luminous element is converted in itswavelength by the phosphor. It can also be used as various image displaymaterials shown below, for its excellent characteristics such as heatresistance, UV resistance and transparency.

The examples of the image display materials include: peripheralmaterials of a liquid crystal display such as substrate material,optical guide plate, prism sheet, deflection plate, phase differenceplate, viewing angle-correction film, adhesive and polarizer-protectivefilm of a liquid crystal display; sealant, antireflection film, opticalcorrection film, protective film for housing material or front glass,substitution material for front glass, and adhesive of a color plasmadisplay panel (PDP), which is one of next-generation flat-paneldisplays; substrate material, optical guide plate, prism sheet,deflection plate, phase difference plate, viewing angle-correction film,adhesive and polarizer-protective film of a plasma address liquidcrystal (PALC) display; protective film for front glass, substitutionmaterial for front glass and adhesive of an organic EL(electroluminescence) display; and various film substrates, protectivefilm for front glass, substitution material for front glass and adhesiveof a field emission display (FED).

The semiconductor-device-member formation liquid of the presentinvention is superior in adhesion and it can be laminated by means ofrecoating, which has been difficult for conventionally-known additioncondensation type silicone resins. Making the most of thischaracteristic, a laminar structure having different refractive indexescan be formed by such a method that, for example, a low-refractive-indexlayer of the semiconductor-device-member formation liquid of the presentinvention that consists mainly of methyl group is laminated with ahigh-refractive-index layer that is introduced with zirconia nanoparticles or high-refractive-index organic groups such as phenyl group.This can form a light guiding layer that is highly durable and excellentin adhesion and flexibility easily.

The present invention has been explained in detail above with referenceto specific embodiments. However, it is evident to those skilled in theart that various modifications can be added thereto without departingfrom the intention and the scope of the present invention.

The present application is based on Japanese Patent Application (No.2006-225410) filed on Aug. 22, 2006, Japanese Patent Application (No.2006-226856) filed on Aug. 23, 2006, Japanese Patent Application (No.2007-216451) filed on Aug. 22, 2007, and Japanese Patent Application(No. 2007-216452) filed on Aug. 22, 2007, and their entireties areincorporated herewith by reference.

1. A method for producing a curable organopolysiloxane composition for asemiconductor device, the curable organopolysiloxane composition forminga siloxane bond when being cured, the method comprising polycondensatinga polysiloxane oligomerconsisting only of bifunctional silicon andhaving a molecular weight of 400 or larger with a silane monomercomprising tri- or more functional silicon or with a polysiloxaneoligomer containing tri- or more functional silicon, the curableorganopolysiloxane composition containing a component having a molecularweight of 800 or smaller at a proportion of, in areal ratio of GPC, 10%or less.
 2. The method according to claim 1, wherein the material to bepolycondensated in the polycondensating includes the polysiloxaneoligomer consisting only of bifunctional silicon and having a molecularweight of 400 or larger at 50 wt % or more to the total weight of thematerial.
 3. The method according to claim 1, wherein the polysiloxaneoligomer consisting only of bifunctional silicon and having a molecularweight of 400 or larger includes a polysiloxane consisting only ofbifunctional silicon and having silanols at the both terminals.
 4. Themethod according to claim 1, wherein the polysiloxane oligomerconsisting only of bifunctional silicon and having a molecular weight of400 or larger includes a polydimethylsiloxane having silanols at theboth terminals.
 5. The method according to claim 1, wherein thepolysiloxane oligomer consisting only of bifunctional silicon and havinga molecular weight of 400 or larger includes adiphenylsiloxane-dimethylsiloxane copolymer having silanols at the bothterminals.
 6. The method according to claim 1, wherein the polysiloxaneoligomer consisting only of bifunctional silicon and having a molecularweight of 400 or larger includes a polydiphenylsiloxane having silanolsat the both terminals.
 7. The method according to claim 1, wherein thepolycondensating uses an organometallic compound catalyst.
 8. The methodaccording to claim 1, further comprising, after the polycondensating,distilling the solvent.
 9. The method according to claim 1, furthercomprising, after the polycondensating, mixing inorganic particle. 10.The method according to claim 1, further comprising, after thepolycondensating, adding phosphor particle.
 11. A method for producing acurable organopolysiloxane composition for a semiconductor device, thecurable organopolysiloxane composition forming a siloxane bond whenbeing cured, the method comprising: polycondensating a polysiloxaneoligomer consisting only of bifunctional silicon and having silanols atthe both ends with a silane monomer comprising tri- or more functionalsilicon and having an alkoxy group or with a polysiloxane oligomercontaining tri- or more functional silicon and having an alkoxy group;and removing alcohol generated in the polycondensation, wherein a ratiorepresented by {(the number of alkoxy groups)/(the number ofsilanols+the number of alkoxy groups)}×100(%) after the distilling is 0%or more and 50% or less.
 12. The method according to claim 11, whereinthe polysiloxane oligomer consisting only of bifunctional silicon andhaving silanols at the both ends includes polydimethylsiloxane.
 13. Themethod according to claim 11, wherein the polysiloxane oligomerconsisting only of bifunctional silicon and having silanols at the bothends includes a diphenylsiloxane-dimethylsiloxane copolymer.
 14. Themethod according to claim 11, wherein the polysiloxane oligomerconsisting only of bifunctional silicon and having silanols at the bothends includes polydiphenylsiloxane.
 15. The method according to claim11, wherein the polycondensating uses an organometallic compoundcatalyst.
 16. The method according to claim 11, further comprising,after the polycondensating, mixing inorganic particle.
 17. The methodaccording to claim 11, further comprising, after the polycondensating,adding phosphor particle.
 18. A curable organopolysiloxane compositionfor a semiconductor device, the curable organopolysiloxane compositionforming a siloxane bond when being cured, the compound comprising apolycondensate obtained by polycondensating a polysiloxane oligomerconsisting only of bifunctional silicon and having a molecular weight of400 or larger with a silane monomer comprising tri- or more functionalsilicon or with a polysiloxane oligomer containing tri- or morefunctional silicon, the curable organopolysiloxane compositioncontaining a component having a molecular weight of 800 or smaller at aproportion of, in areal ratio of GPC, 10% or less.
 19. The curableorganopolysiloxane composition according to claim 18, having a viscosityat 25° C. of 20 mPa·s or more and 1500 mPa·s or less.
 20. The curableorganopolysiloxane composition according to claim 18, wherein thepolysiloxane oligomer consisting only of bifunctional silicon and havinga molecular weight of 400 or larger includes polydimethylsiloxane. 21.The curable organopolysiloxane composition according to claim 18,wherein the polysiloxane oligomer consisting only of bifunctionalsilicon and having a molecular weight of 400 or larger includesdiphenylsiloxane-dimethylsiloxane copolymer.
 22. The curableorganopolysiloxane composition according to claim 18, wherein thepolysiloxane oligomer consisting only of bifunctional silicon and havinga molecular weight of 400 or larger includes polydiphenylsiloxane. 23.The curable organopolysiloxane composition according to claim 18,further comprising inorganic particle.
 24. The curableorganopolysiloxane composition according to claim 18, further comprisingphosphor particle.
 25. A curable organopolysiloxane composition for asemiconductor device, the curable organopolysiloxane composition forminga siloxane bond when being cured, the curable organopolysiloxanecomposition comprising a polycondensate obtained by polycondensating apolysiloxane oligomer consisting only of bifunctional silicon and havingsilanols at the both ends with a silane monomer comprising tri- or morefunctional silicon and having an alkoxy group or with a polysiloxaneoligomer containing tri- or more functional silicon and having an alkoxygroup, wherein the curable organopolysiloxane composition has a ratiorepresented by {(the number of alkoxy groups)/(the number ofsilanols+the number of alkoxy groups)}×100(%) of 0% or more and 50% orless.
 26. The curable organopolysiloxane composition according to claim25, having a viscosity at 25° C. of 20 mPa·s or more and 1500 mPa·s orless.
 27. The curable organopolysiloxane composition according to claim25, wherein the polysiloxane oligomer consisting only of bifunctionalsilicon and having silanols at the both ends includespolydimethylsiloxane.
 28. The curable organopolysiloxane compositionaccording to claim 25, wherein the polysiloxane oligomer consisting onlyof bifunctional silicon and having silanols at the both ends includesdiphenylsiloxane-dimethylsiloxane copolymer.
 29. The curableorganopolysiloxane composition according to claim 25, wherein thepolysiloxane oligomer consisting only of bifunctional silicon and havingsilanols at the both ends includes polydiphenylsiloxane.
 30. The curableorganopolysiloxane composition according to claim 25, further comprisinginorganic particle.
 31. The curable organopolysiloxane compositionaccording to claim 25, further comprising phosphor particle.
 32. Amethod for producing a semiconductor device, the method comprisingcuring the curable organopolysiloxane composition defined in one ofclaim 18.